bluuebunny/crossref_metadata_2025 huggingface dataset:
Anthropogenic and climate‐driven water depletion in Asia
Authors: Yi Shuang , Sun Wenke , Feng Wei , Chen Jianli
Published: August 2016

Anthropogenic depletion of terrestrial water storage (TWS) can be alleviated in wet years and intensified in dry years, and this wet/dry pattern spanning seasons to years is termed climate variability. However, the anthropogenic and climate‐driven changes have not been isolated in previous studies; thus, the estimated trend of changes in TWS is strongly dependent on the study period. Here we try to remove the influence of climate variability from the estimation of the anthropogenic contribution, which is an indicator of the environmental burden and important for TWS projections. Toward this end, we propose a linear relationship between the variation in water storage and precipitation. Factors related to the sensitivity of water storage to precipitation are given to correct for the climate variability, and the anthropogenic depletion of terrestrial water and groundwater in Asia is estimated to be −187 ± 38 Gt/yr and −100 ± 47 Gt/yr, respectively.
Poroelastic stress triggering of the December 2013 Crooked Lake, Alberta, induced seismicity sequence
Authors: Deng Kai , Liu Yajing , Harrington Rebecca M.
Published: August 2016

The Crooked Lake area in Central Alberta, Canada, became seismically active in December 2013 with a sequence of earthquakes Mw 2.0 and higher. The earthquakes are suspected to be induced by hydraulic fracturing in nearby horizontal wells due to their strong spatiotemporal correlation. To investigate the physical mechanism of the induced seismicity near Crooked Lake, we calculate stress and pore pressure perturbations resulting from high‐rate multistage fluid injection in the framework of linear poroelasticity. The calculated perturbations are used for seismic risk analysis based on the Coulomb failure criterion. Results show that most seismicity is within a positive Coulomb stress change regime, indicating that failure is promoted by injection of fluid. By comparing Coulomb stress results for different parameter settings, we show that elastic response of the solid matrix, instead of fluid diffusion, is more likely the dominant factor for the induced earthquakes shortly after fluid injection.
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

The 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

Objective

To 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.

Methods

We 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.

Results

PSMD 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.

Interpretation

PSMD 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.
Synthesis of magnetically recyclable Fe3O4@[(EtO)3Si–L1H]/Pd(II) nanocatalyst and application in Suzuki and Heck coupling reactions
Authors: Keypour Hassan , Saremi Shokoufeh Ghahri , Noroozi Mohammad , Veisi Hojat
Published: August 2016

A Pd(II) Schiff base complex as an efficient and highly heterogeneous catalyst was developed by immobilization of a palladium complex on the surface of modified Fe3O4 magnetite nanoparticles. These surface‐modified nanoparticles were characterized using various techniques such as transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, vibrating sample magnetometry, elemental analysis and Fourier transform infrared spectroscopy. The palladium catalyst exhibited efficient catalytic activity in Suzuki and Heck coupling reactions. This method has notable advantages such as excellent chemoselectivity, mild reaction conditions, short reaction times and excellent yields. The yields of the products were in the range 85–100%. Also, the nanocatalyst can be easily recovered with a permanent magnet and reused at least five times without noticeable leaching or loss of its catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.
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

A 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

We 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

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

We 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.
Evaluation of Antioxidant, Anticholinesterase, and Antidiabetic Potential of Dry Leaves and Stems in Tamarix aphylla Growing Wild in Tunisia
Authors: Mahfoudhi Adel , Grosso Clara , Gonçalves Rui F. , Khelifi Eltaief , Hammami Saoussen , Achour Sami , Trabelsi‐Ayadi Malika , Valentão Patrícia , Andrade Paula B. , Mighri Zine
Published: August 2016

Tamarix aphylla (L.) Karst. has a wide geographic distribution and was employed in traditional medicine as astringent, anti‐rheumatic and to treat fever. T. aphylla leaves and stems extracts were studied from both chemical and biological points of view to assess the antidiabetic, anticholinesterase and antioxidant potential of this species. The HPLC/Diode Array Detector (DAD) analysis showed the presence of 14 phenolic compounds (gallic, caffeic, p‐coumaric, ferulic and ellagic acids, kaempferol, quercetin, quercetin 3‐O‐galactoside and six flavonol derivatives). This is the first study reporting a comparative study of the biological activities of different extracts from T. aphylla. High activities were obtained against DPPH radical, superoxide anion radical () and nitric oxide radical (•NO) in a concentration‐dependent manner, the most active extracts being the polar ones. T. aphylla also showed moderate protective effects against acetylcholinesterase, but no effects were observed against butyrylcholinesterase. Against α‐glucosidase the MeOH extracts displayed IC50 values from 8.41 to 24.81 μg/ml.
Comparison of Phytochemical Composition and Biological Activities of Rubus ulmifolius Extracts Originating from Four Regions of Tunisia
Authors: Tabarki Sonia , Aouadhi Chedia , Mechergui Kaouther , Hammi Khaoula Mkadmini , Ksouri Riadh , Raies Aly , Toumi Lamjed
Published: August 2016

In the current study, the phenolic composition, antioxidant and antimicrobial activities of extracts from Rubus ulmifolius Schott leaves harvested in four localities (Sejnen, Tabarka, Faija and Ain drahem) in Tunisia were investigated for the first time. Great differences were found for the chemical composition, total phenol contents and biological activities among the evaluated extracts. HPLC analysis of methanolic extracts showed that the dominant compounds were kaempferol 3‐O‐rutinoside and naringenine. In addition, significant correlations were observed between antioxidant activities and phenolic contents. In fact, leaves collected from Sejnen presented higher total phenol content (53.32 mg GAE/g DW) and antioxidant activities (IC50 = 39.40 mg/l) than the others samples. All extracts showed significant antimicrobial activity against six used bacteria with the inhibition zones diameters and minimal inhibitory concentration values were in the range of 8 – 16 mm and 6.25 – 25 mg/ml, respectively. The highest antimicrobial activities were recorded in Sejnen extract against Gram‐positive bacteria.
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

Background

Overlapping 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.
Interventional re‐opening of a PDA for reverse potts shunt circulation after ADO I implantation in a child
Authors: Schubert Stephan , Peters Björn , Berger Felix
Published: August 2016

We report interventional re‐opening of a PDA for reverse Potts shunt circulation 12 months after closure in a 3.8 year old child, suffering from right ventricular (RV) failure due to suprasystemic pulmonary artery hypertension (PAH) after ADO I implantation. After ex vivo simulation, perforation through the mesh of the ADO I with the use of transseptal needle, wire looping (AO‐PA), balloon dilatation, stent implantation (Palmaz 6 mm) and post dilatation, a reverse Pott‐shunt circulation was established. A follow‐up period of 11 months was achieved with preserved RV function and reverse Pott shunt circulation maintained a post ductal saturation of 94–88%. © 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

Resource‐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

A 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

Subphthalocyanine (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

The 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

Twisted 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

Herein, 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

This 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

Copper/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.
Preparation of Magnesium, Cobalt and Nickel Ferrite Nanoparticles from Metal Oxides using Deep Eutectic Solvents
Authors: Söldner Anika , Zach Julia , Iwanow Melanie , Gärtner Tobias , Schlosser Marc , Pfitzner Arno , König Burkhard
Published: August 2016

Natural deep eutectic solvents (DESs) dissolve simple metal oxides and are used as a reaction medium to synthesize spinel‐type ferrite nanoparticles MFe2O4 (M=Mg, Zn, Co, Ni). The best results for phase‐pure spinel ferrites are obtained with the DES consisting of choline chloride (ChCl) and maleic acid. By employing DESs, the reactions proceed at much lower temperatures than usual for the respective solid‐phase reactions of the metal oxides and at the same temperatures as synthesis with comparable calcination processes using metal salts. The method therefore reduces the overall required energy for the nanoparticle synthesis. Thermogravimetric analysis shows that the thermolysis process of the eutectic melts in air occurs in one major step. The phase‐pure spinel‐type ferrite particles are thoroughly characterized by X‐ray diffraction, diffuse‐reflectance UV/Vis spectroscopy, and scanning electron microscopy. The properties of the obtained nanoparticles are shown to be comparable to those obtained by other methods, illustrating the potential of natural DESs for processing metal oxides.
Mere newness: Decline of movie preference over time
Authors: Ho Jason Y. C. , Krider Robert E. , Chang Jennifer
Published: August 2016

We investigate the possibility that an individual‐level decline in preference over time is responsible for the well‐known decline in a movie's revenues after opening. In the first part of this study, using a Canadian panel we show that such a decline does indeed occur in both individual consumers’ anticipated liking of movies, and in actual movie choice. The second part explores the mere newness effect building on the fact that new products carry both private and social values, and proposes that these values decay continuously over time. Capitalizing on the notion that characteristics of market mavens interact differently with private and social values, we develop and show support for hypotheses based on the proposed mechanism. Copyright © 2016 ASAC. Published by John Wiley & Sons, Ltd.
Patient function, long‐term survival, and use of surgery in patients with kidney cancer
Authors: Tan Hung‐Jui , Chamie Karim , Daskivich Timothy J. , Litwin Mark S. , Hu Jim C.
Published: August 2016

BACKGROUND

Beyond age and comorbidity, functionality can shape the long‐term survival potential of patients with cancer. Accordingly, herein the authors compared mortality and receipt of cancer‐directed surgery according to patient function among older adults with kidney cancer.

METHODS

Using Surveillance, Epidemiology, and End Results (SEER)‐Medicare data from 2000 through 2009, the authors studied 28,326 elderly subjects with primary kidney cancer. Patient function was quantified using function‐related indicators, claims indicative of dysfunction and disability. Adjusting for patient and cancer characteristics, competing risk regression was used to assess the relationship between function‐related indicator count and cause‐specific mortality and then generalized estimating equations were used to quantify the probability of surgery.

RESULTS

A total of 13,619 adult patients (48.1%) with at least 1 function‐related indicator were identified. A higher indicator category was associated with older age, greater comorbidity, female sex, unmarried status, lower socioeconomic status, and higher stage of disease (P<.001). Compared with patients with an indicator count of 0, those with an indicator count of 1 (hazard ratio, 1.10; 95% confidence interval [95% CI], 1.04‐1.16) and ≥2 (hazard ratio, 1.46; 95% CI, 1.39‐1.53) were found to have higher other‐cause mortality. Conversely, kidney cancer mortality varied minimally with patient function. Patients with ≥ 2 indicators received cancer‐directed surgery less often than those without disability (odds ratio, 0.61; 95% CI, 0.56‐0.66), although treatment probabilities remained high for patients with locoregional disease and low for those with metastatic cancer.

CONCLUSIONS

Among older adults with kidney cancer, functional health stands as a significant predictor of long‐term survival. However, receipt of cancer‐directed surgery appears largely determined by cancer stage. Patient function should be considered more heavily when determining treatment for older adults with kidney cancer. Cancer 2016;122:3776–3784. © 2016 American Cancer Society.
Quantized Feature with Angular Displacement for Activity Recognition
Authors: YAMABE TOMOAKI , KATAOKA HIROKATSU , NAKAMURA AKIO
Published: August 2016

We propose quantized feature with angular displacement for pose‐based activity recognition. We calculate a three‐dimensional (3D) joint angle from three postural coordinates. The angular displacement should be quantized since joint angle includes errors due to system noises and similar posture. To investigate appropriate features, we propose four kinds of quantization levels; binarization, ternarization, quaternarization, and quinarization. We apply quantized features in order to improve pose‐based activity recognition with the UTKinect‐Action Dataset. In the experiment, we show the appropriate feature for activity recognition. As the result, the ternarized feature achieves the highest recognition rate in average. The recognition rate of trials with ternarized feature is improved 2.4% to one with no‐quantized feature, and 1.8% to conventional method.
A Click Ligation Based on SuFEx for the Metal‐Free Synthesis of Sugar and Iminosugar Clusters
Authors: Zelli Renaud , Tommasone Stefano , Dumy Pascal , Marra Alberto , Dondoni Alessandro
Published: August 2016

Although the preparation of anomeric glycosylsulfonyl fluoride was unsuccessful, a tetra‐O‐acetylated C‐glucosylpropanesulfonyl fluoride was synthesized starting from the corresponding thioacetate via sulfonate formation as the key intermediate. This sulfonyl fluoride was a bench‐stable product that reacted promptly with primary and secondary alkylamines at 80 °C to give the corresponding sulfonamides in good yield. On the other hand, the same fluoride was inert toward arylamines whereas its precursor, the sulfonyl chloride, showed good reactivity. Another limitation of the acetylated sugar sulfonyl fluoride was its lack of reactivity with a multivalent aminated calixarene, this being due to acetyl transfer from the carbohydrate moiety to the amino groups of the scaffold. Fortunately, the tetra‐O‐benzylated C‐glucosylpropanesulfonyl fluoride, prepared by the same reaction sequence employed for the synthesis of the acetylated analogue, reacted with the tetra‐aminopropyl‐calix[4]arene to afford the corresponding sulfonamide‐linked sugar cluster in high isolated yield. A similar approach to the synthesis of calixarene‐based iminosugar clusters was unsuccessful because 1‐deoxynojirimycin sulfonyl fluoride derivatives could not be generated. However, a tetra‐propylsulfonyl fluoride calixarene, obtained from the free‐OH calix[4]arene through a three‐step reaction sequence, underwent clean coupling with both C‐glucosylpropylamine and N‐aminopentyl‐1‐deoxy‐deoxynojirimycin derivatives to give the corresponding tetravalent sugar and iminosugar clusters. This metal‐free click reaction may constitute a valuable tool in the arsenal of ligation tools for the synthesis of multivalent carbohydrate architectures.
Glycosyl ortho‐Methoxybenzoates: Catalytically Activated Glycosyl Donors with an Easily Removable and Recyclable Leaving Group
Authors: Kristensen Steffan K. , Salamone Stéphane , Rasmussen Michelle R. , Marqvorsen Mikkel H. S. , Jensen Henrik H.
Published: August 2016

We describe the β‐ortho‐methoxybenzoate as a shelf stable and practical C‐1 nucleofuge for catalytic chemical glycosylation in which the benzoic acid by‐product can be easily removed, reisolated, and potentially recycled after the glycosylation reaction. This new type of glycosyl donor can be efficiently activated by a range of promoters, including Bi(OTf)3, Fe(OTf)3, TMSOTf (TMS = trimethylsilyl), and triflic acid, with low (<10 mol‐%) catalyst loadings. The donor shows higher reactivity than analogous benzoate, p‐methoxybenzoate and p‐cyano‐o‐methoxybenzoate donors. In glycosylation reactions with o‐methoxybenzoate donors, the yields of disaccharide products were good to excellent for various glycosyl acceptors, including a carbohydrate‐based secondary alcohol. Furthermore, β‐selective mannosylation was achieved with a Crich‐type donor at 0 °C to ambient temperature, without donor preactivation. The donor was also used for the first step of a one‐pot two‐step glycosylation to obtain a trisaccharide; the second coupling involved activation of a thioglycoside with NIS/TMSOTf (NIS = N‐iodosuccinimide). We believe that this offers a good alternative to current protocols.
NHC‐Catalyzed Benzylic Csp³–H Bond Activation of Alkylarenes and N‐Benzylamines for the Synthesis of 3H‐Quinazolin‐4‐ones: Experimental and Theoretical Study
Authors: Alanthadka Anitha , Devi E. Sankari , Nagarajan Subbiah , Sridharan Vellaisamy , Suvitha Ambigapathy , Maheswari C. Uma
Published: August 2016

An N‐heterocyclic carbene catalyzed benzylic Csp³–H bond activation of alkylarenes and N‐benzylamines under metal‐free conditions was developed. This organocatalyzed oxidative transformation afforded the corresponding carbonyl derivatives in good to excellent yields. A variety of alkylarenes and N‐benzylamines were tolerated under the optimized reaction conditions. The established method was further extended to the synthesis of biologically important 3H‐quinazolin‐4‐ones in good yields. For example, NPS 53574, a potent calcium receptor antagonist, was successfully synthesized by using this oxidative protocol. DFT studies show that the benzylic C–H bond activation proceeds through the nucleophilic attack of the free carbene on the benzylic carbon atom.
Twisted C=C Double Bonds with Very Low Rotational Barriers in Dioxanediones and Isoxazolones Determined by Low‐Temperature Dynamic NMR Spectroscopy and Computational Chemistry
Authors: Wentrup Curt , Koch Rainer , Kleinpeter Erich
Published: August 2016

Extremely low rotational barriers for ethylenic C=C double bonds in the range 5–17 kcal/mol have been measured by low temperature 1H and 13C NMR spectroscopy and confirmed by calculations at the M06‐2X level for 5‐methylene‐1,3‐dioxane‐4,6‐diones (Meldrum's acid derivatives) and 4‐methyleneisoxazol‐5(4H)‐ones. The barriers are ascribed to the push‐pull (donor‐acceptor) nature of the alkenes. A correlation between the calculated C=C bond lengths and the ratios of electron occupancies in the ethylenic π and π* orbitals (the π/π* quotient) constitutes a useful measure of the push‐pull character.
Indium Tin Oxide Microsystem for Electrochemical Detection of Exocytosis of Migratory Dendritic Cells
Authors: Liu Xiaoqing , Bretou Marine , Lennon‐Duménil Ana‐Maria , Lemaître Frédéric , Guille‐Collignon Manon
Published: August 2016

The design, fabrication and test of an indium tin oxide (ITO) microdevice to investigate exocytotic behaviors of migratory dendritic cells (DCs) in confined three‐dimensional environment were reported in this work. Indeed, immature DCs were able to migrate into micro‐fabricated biocompatible polydimethylsiloxane (PDMS) channels that mimic their natural constrained environment of tissues for patrolling in search of danger associated antigens through an endocytotic process called macropinocytosis. In order to coordinate membrane trafficking and prevent cell volume increment, DCs will release part of their contents back to the extracellular medium while migrating. Through electrochemical measurements, we demonstrated that exocytotic events of migratory DCs could be monitored by our ITO microdevice. In addition, the transparency of ITO electrode should facilitate future combining assays of exocytosis with other fluorescence‐based measurements of cell physiology.
On‐line coupling of sample preconcentration by LVSEP with gel electrophoretic separation on T‐channel chips
Authors: Kitagawa Fumihiko , Kinami Saeko , Takegawa Yuuki , Nukatsuka Isoshi , Sueyoshi Kenji , Kawai Takayuki , Otsuka Koji
Published: August 2016

To achieve an on‐line coupling of the sample preconcentration by a large‐volume sample stacking with an electroosmotic flow pump (LVSEP) with microchip gel electrophoresis (MCGE), a sample solution, a background solution for LVSEP and a sieving solution for MCGE were loaded in a T‐form channel and three reservoirs on PDMS microchips. By utilizing the difference in the flow resistance of the two channels, a low‐viscosity sample and a viscous polymer solution were easily introduced into the LVSEP and MCGE channels, respectively. Fluorescence imaging of the sequential LVSEP‐MCGE processes clearly demonstrated that a faster stacking of anionic fluorescein and successive introduction into the MCGE channel can be carried out on the T‐channel chip. To evaluate the preconcentration performance, a conventional MCZE analysis of fluorescein on the cross‐channel chip was compared with LVSEP‐MCGE on the short T‐channel chip, and as a result that the value of sensitive enhancement factor (SEF) was estimated to be 370. The repeatability of the peak height was good with the RSD value of 3.2%, indicating the robustness of the enrichment performance. In the successive LVSEP‐MCGE analysis of φX174/HaeIII digest, the DNA fragments were well enriched to a sharp peak in the LVSEP channel, and they were separated in the MCGE channel, whose electropherogram was well‐resembled with that in the conventional MCGE. The values of SEF for the DNA fragments were calculated to be ranging from 74 to 108. Thus, the successive LVSEP‐MCGE analysis was effective for both preconcentrating and separating DNA fragments.
Development of an enantioselective capillary electrophoretic method for the simultaneous determination of montelukast enantiomeric and diastereoisomeric forms and its main degradation product
Authors: Flor Sabrina , Huala Juan Martin , Tripodi Valeria , Lucangioli Silvia
Published: August 2016

A stereoselective CD‐MEKC system has been developed for the quality control of Montelukast (MK), commercialized as a pure enantiomer. The proposed method is the first one that allows the simultaneous determination of MK, its enantiomeric form, diasteroisomers and its main degradation compound (MK sulphoxide). CD‐MEKC system is composed of 10 mM SDS, 10 mM sulfobutylether‐β‐CD, 10 mM TM‐β‐CD, and 20 mM borate buffer at pH 9.0. Combination of these two CDs allows high baseline enantioresolution between MK and its enantiomeric impurity, but also, between the diasteroisomeric forms. Moreover, a multivariate design was applied to optimize operational parameters. The method was designed to meet with requirements of the official pharmacopoeias and fully validated according to international guidelines. Linearity of MK was demonstrated in the range from 10.0 to 100.0 μg/mL (r2 = 0.9908) with a LOD and LOQ of 0.30 and 0.90 μg/mL, respectively. Intra and interday precision were evaluated and RSD values were below 2%, and also, accuracy expressed as percentage of recovery was in a range from 99.0 to 101.9 for the three assayed levels. The method allows determining 0.02% w/w of the enantiomeric and diasteroisomeric impurities, and 0.01% w/w of MK sulphoxide. Robustness was evaluated by a Plackett and Burman design. Finally, the CD‐MEKC system was successfully applied to the determination of related substances in MK bulk drug and its quantification in two pediatric pharmaceutical dosage forms.
What becomes of people admitted to acute old age psychiatry wards? An exploration of factors affecting length of stay, delayed discharge and discharge destination
Authors: Tucker Sue , Hargreaves Claire , Wilberforce Mark , Brand Christian , Challis David
Published: August 2016

Objectives

The study sought to identify the variables associated with increased length of stay on old age psychiatry inpatient wards. It also explored the factors related to delayed discharge and the likelihood of patients admitted from home returning there.

Methods

Data were collected on the sociodemographic, clinical and service receipt characteristics of a 6‐month series of admissions to seven wards in England in 2010/2011. The cohort was followed for a 9‐ to 11‐month period. The relationship between patients' status on admission and the specified outcome variables was explored.

Results

Information was collected on 216 admissions, of whom 165 were discharged in the study period. Mean length of stay was 64 days. Female gender, higher dependency, greater challenging behaviour and locality predicted extended stay. Forty per cent of cases experienced delayed discharge. Better physical health, more cognitive impairment, receipt of social care and locality were associated with delayed discharge. The vast majority of patients admitted from home returned there. Younger patients and patients with less dependency, cognitive impairment and challenging behaviour had a higher likelihood of returning home. Patients receiving social care or admitted because of carer stress, a risk of self‐neglect, accidental self‐harm or abuse/exploitation were less likely to return home.

Conclusions

The study provides a useful starting point for identifying cases on which future efforts to improve inpatient outcomes might centre and suggests local rather than national responses may be needed. It also highlights an urgent need for a national focus on the scope, purpose and effectiveness of acute inpatient care. Copyright © 2016 John Wiley & Sons, Ltd.