bluuebunny/crossref_metadata_2025_split huggingface dataset:
3D Framework DNA Origami with Layered Crossovers
Authors: Hong Fan , Jiang Shuoxing , Wang Tong , Liu Yan , Yan Hao 
Published: September 2016

AbstractDesigner DNA architectures with nanoscale geometric controls provide a programmable molecular toolbox for engineering complex nanodevices. Scaffolded DNA origami has dramatically improved our ability to design and construct DNA nanostructures with finite size and spatial addressability. Here we report a novel design strategy to engineer multilayered wireframe DNA structures by introducing crossover pairs that connect neighboring layers of DNA double helices. These layered crossovers (LX) allow the scaffold or helper strands to travel through different layers and can control the relative orientation of DNA helices in neighboring layers. Using this design strategy, we successfully constructed four versions of two‐layer parallelogram structures with well‐defined interlayer angles, a three‐layer structure with triangular cavities, and a 9‐ and 15‐layer square lattices. This strategy provides a general route to engineer 3D framework DNA nanostructures with controlled cavities and opportunities to design host–guest networks analogs to those produced with metal organic frameworks.
A Boryl‐Substituted Diphosphene: Synthesis, Structure, and Reaction with n‐Butyllithium To Form a Stabilized Adduct by pπ‐pπ Interaction
Authors: Asami Shun‐suke , Okamoto Masafumi , Suzuki Katsunori , Yamashita Makoto 
Published: September 2016

AbstractA boryl‐substituted diphosphene was synthesized through the nucleophilic borylation of PCl3 with a borylzinc reagent, followed by a reduction with Mg. A combined analysis of the resulting diboryldiphosphene by single‐crystal X‐ray diffraction, DFT calculations, and UV/Vis spectroscopy revealed a σ‐electron‐donating effect for the boryl substituent that was slightly weaker than that of the 2,4,6‐tri‐tert‐butylphenyl (Mes*) ligand. The reaction of this diboryldiphosphene with nBuLi afforded a boryl‐substituted phosphinophosphide that was, in comparison with the thermally unstable Mes*‐substituted diaryldiphosphene, stabilized by a π‐electron‐accepting effect of the boryl substituent.
Novel tools for early detection of a global aquatic invasive, the zebra mussel Dreissena polymorpha
Authors: Ardura Alba , Zaiko Anastasija , Borrell Yaisel J. , Samuiloviene Aurelija , Garcia‐Vazquez Eva 
Published: September 2016

Abstract

This study presents a species‐specific DNA‐based marker for detection of the zebra mussel Dreissena polymorpha, recognized as one of the worst invasive species worldwide.
The marker was developed in silico and experimentally tested on environmental samples. Gel and capillary electrophoreses for visualization of the PCR products were compared.
Marker specificity and sensitivity were assessed in vitro by cross‐amplifications and serial dilutions, respectively. The method allows detecting at least 0.7 ng of Dreissena DNA per μL and cross‐species amplification was not found in any case.
Next‐generation sequencing (NGS) metabarcoding (PCR amplification and massive sequencing of a DNA barcode) was used as an independent method for verifying presence of Dreissena DNA molecules in environmental plankton samples collected from the south‐eastern Baltic Sea.
The consistency between NGS results reporting presence of Dreissena and positive PCR amplification of the marker from the plankton samples confirmed the efficacy of this highly reproducible, fast, cheap and technically easy method.
Copyright © 2016 John Wiley & Sons, Ltd.
A Divergent Approach to the Diastereoselective Synthesis of 3,3‐Disubstituted Oxindoles from Atropisomeric N‐Aryl Oxindole Derivatives
Authors: Nakazaki Atsuo , Mori Ayako , Kobayashi Susumu , Nishikawa Toshio 
Published: September 2016

Abstract3,3‐Disubstituted oxindoles were divergently synthesized by diastereoselective transformations including nucleophilic addition, alkylation, and cycloaddition using common, axially chiral N‐aryl oxindoles. Notably, high diastereoselectivities (up to >95:5) were observed with ortho‐monosubstituted N‐aryl oxindoles to give various oxindole scaffolds, and facile removal of the p‐(benzyloxy)aryl moiety in axially twisted amides was achieved by a mild, two‐step sequence.
Robust Finite‐Time H∞ Control of a Class of Disturbed Systems using Lmi‐Based Approach
Authors: Zhang Xiaoyu , Zhong Jihong , Zhang Quan , Ma Kemao 
Published: September 2016

AbstractIn this paper, the definition of robust finite‐time H∞ control is presented for a class of disturbed systems. Time‐varying norm‐bounded exogenous disturbance is considered in the system. A state feedback controller is designed, via a Linear Matrix Inequalities (LMIs) approach, which ensures that the closed‐loop system is finite‐time bounded (FTB) and reduces the effect of the disturbance input on the controlled output to a prescribed level. The main result, derived by Lyapunov functions, is a sufficient condition for FTB of disturbed systems and the sufficient condition can be reduced to a feasibility problem involving LMIs. Then a DC motor position control problem is simulated as a demonstration for this study. Simulation results are presented to show the effectiveness of the proposed method as a promising approach for controlling similar disturbed systems.
Multicentre study of the impact of morbidity on long-term survival following hepatectomy for intrahepatic cholangiocarcinoma
Authors: Doussot A , Lim C , Gómez-Gavara C , Fuks D , Farges O , Regimbeau J M , Azoulay D , Adam R , Pascal G , Castaing D , Cherqui D , Baulieux J , Mabrut J Y , Ducerf C , Belghiti J , Nuzzo G , Giuliante F , Le Treut Y-P , Hardwigsen J , Pessaux P , Bachellier P , Pruvot F R , Boleslawski E , Rivoire M , Chiche L 
Published: September 2016

Abstract

Background
The impact of morbidity on long-term outcomes following liver resection for intrahepatic cholangiocarcinoma is currently unclear.

Methods
This was a retrospective analysis of all consecutive patients who underwent liver resection for intrahepatic cholangiocarcinoma with curative intent in 24 university hospitals between 1989 and 2009. Severe morbidity was defined as any complication of Dindo–Clavien grade III or IV. Patients with severe morbidity were compared with those without in terms of demographics, pathology, management, morbidity, overall survival, disease-free survival and time to recurrence. Independent predictors of severe morbidity were identified by multivariable analysis.

Results
A total of 522 patients were enrolled. Severe morbidity occurred in 113 patients (21·6 per cent) and was an independent predictor of overall survival (hazard ratio 1·64, 95 per cent c.i. 1·21 to 2·23), as were age at resection, multifocal disease, positive lymph node status and R0 resection margin. Severe morbidity did not emerge as an independent predictor of disease-free survival. Independent predictors of time to recurrence included severe morbidity, tumour size, multifocal disease, vascular invasion and R0 resection margin. Major hepatectomy and intraoperative transfusion were independent predictors of severe morbidity.

Conclusion
Severe morbidity adversely affects overall survival following liver resection for intrahepatic cholangiocarcinoma.
Filtering and storage working memory networks in younger and older age
Authors: Vellage Anne‐Katrin , Becke Andreas , Strumpf Hendrik , Baier Bernhard , Schönfeld Mircea Ariel , Hopf Jens‐Max , Müller Notger G. 
Published: September 2016

AbstractIntroductionWorking memory (WM) is a multi‐component model that among others involves the two processes of filtering and storage. The first reflects the necessity to inhibit irrelevant information from entering memory, whereas the latter refers to the active maintenance of object representations in memory. In this study, we aimed at a) redefining the neuronal networks sustaining filtering and storage within visual working memory by avoiding shortcomings of prior studies, and b) assessing age‐related changes in these networks.MethodsWe designed a new paradigm that strictly controlled for perceptual load by presenting the same number of stimuli in each of three conditions. We calculated fMRI contrasts between a baseline condition (low filter and low storage load) and conditions that posed high demands on filtering and storage, respectively, in large samples of younger (n = 40) and elder (n = 38) participants.ResultsOur approach of comparing contrasts between groups revealed more extensive filter and storage WM networks than previous studies. In the younger group, filtering involved the bilateral insulae, the right occipital cortex, the right brainstem, and the right cerebellum. In the elder group, filtering was associated with the bilateral insulae, right precuneus, and bilateral ventromedial prefrontal cortex. An extensive neuronal network was also found during storage of information in the bilateral posterior parietal cortex, the left ventromedial prefrontal cortex, and the right precuneus in the younger participants. In addition to these brain regions, elder participants recruited the bilateral ventral prefrontal cortex, the superior, middle and inferior and temporal cortex, the left cingulum and the bilateral parahippocampal cortex.ConclusionsIn general, elder participants recruited more brain regions in comparison to younger participants to reach similar accuracy levels. Furthermore, in elder participants one brain region emerged in both contrasts, namely the left ventromedial prefrontal cortex. Hence, elder participants seem to routinely recruit this brain region in demanding tasks, irrespective of whether filtering or storing is challenged.
Associations between cancer and Alzheimer's disease in a U.S. Medicare population
Authors: Freedman Daryl Michal , Wu Jincao , Chen Honglei , Kuncl Ralph W. , Enewold Lindsey R. , Engels Eric A. , Freedman Neal D. , Pfeiffer Ruth M. 
Published: September 2016

AbstractSeveral studies have reported bidirectional inverse associations between cancer and Alzheimer's disease (AD). This study evaluates these relationships in a Medicare population. Using Surveillance, Epidemiology, and End Results (SEER) linked to Medicare data, 1992–2005, we evaluated cancer risks following AD in a case–control study of 836,947 cancer cases and 142,869 controls as well as AD risk after cancer in 742,809 cancer patients and a non‐cancer group of 420,518. We applied unconditional logistic regression to estimate odds ratios (ORs) and Cox proportional hazards models to estimate hazards ratios (HRs). We also evaluated cancer in relation to automobile injuries as a negative control to explore potential study biases. In the case–control analysis, cancer cases were less likely to have a prior diagnosis of AD than controls (OR = 0.86; 95% CI = 0.81–0.92). Cancer cases were also less likely than controls to have prior injuries from automobile accidents to the same degree (OR = 0.83; 95% CI = 0.78–0.88). In the prospective cohort, there was a lower risk observed in cancer survivors, HR = 0.87 (95% CI = 0.84–0.90). In contrast, there was no association between cancer diagnosis and subsequent automobile accident injuries (HR = 1.03; 95% CI = 0.98–1.07). That cancer risks were similarly reduced after both AD and automobile injuries suggest biases against detecting cancer in persons with unrelated medical conditions. The modestly lower AD risk in cancer survivors may reflect underdiagnosis of AD in those with a serious illness. This study does not support a relationship between cancer and AD.
Effect of Particle Size upon Pt/SiO2 Catalytic Cracking of n‐Dodecane under Supercritical Conditions: In situ SAXS and XANES Studies
Authors: Lee Sungwon , Lee Sungsik , Kumbhalkar Mrunmayi D. , Wiaderek Kamila M. , Dumesic James , Winans Randall E. 
Published: September 2016

AbstractThe endothermic cracking and dehydrogenation of n‐dodecane is investigated over well‐defined nanometer size platinum catalysts supported on SiO2 to study the particle size effects in the catalytic cracking reaction, with simultaneous in situ monitoring of the particle size and oxidation state of the working catalysts by in situ SAXS (small angle X‐ray scattering) and XAS (X‐ray absorption spectroscopy). The selectivity toward olefins products was found dominant in the 1 nm size platinum catalysts, whereas paraffins are dominant in the 2 nm catalysts. This reveals a strong correlation between catalytic performance and catalyst size as well as the stability of the nanoparticles in supercritical condition of n‐dodecane. The presented results suggest that controlling the size and geometric structure of platinum nanocatalysts could lead to a fundamentally new level of understanding of nanoscale materials by monitoring the catalysts in realistic reaction conditions.
Bimetallic and Plasmonic Ag–Au on TiO2 for Solar Water Splitting: An Active Nanocomposite for Entire Visible‐Light‐Region Absorption
Authors: Patra Kshirodra K. , Gopinath Chinnakonda S. 
Published: September 2016

AbstractThe current study demonstrates a potential method for maximum utilization of the entire visible light region of the solar spectrum by designing a plasmonic‐metals semiconductor composite. A combination of Ag+Au nanoclusters would broaden the visible‐light absorption at least between 400 and 650 nm. This hypothesis was evaluated through solar water splitting (SWS) activity of Au–TiO2, Ag–TiO2, and Ag on Au‐TiO2 (AgAuT) composites. AgAuT bimetallic nanocomposite shows the maximum apparent quantum yield of 3.3 % with hydrogen generation (718 μmol h.g−1) from aqueous methanol, and overall water splitting activity (7 μmol g.h−1, AQY=0.04 %) under one sun conditions. Enhanced photocatalytic activity of AgAuT is partly attributed to the formation of hot electrons. A thin layer of Ag coating on Au particles leads to a core–shell morphology with Au in the core. Fermi level equilibration between metal and titania, and Schottky junction formation are directly demonstrated. The strong electronic interaction between Ag and Au, and with TiO2 is evident from its electron rich character and confirmed by Raman spectroscopy, X‐ray photoelectron spectroscopy, photoluminescence, and high‐resolution TEM measurements. Electronic factors seem to be responsible for the high rate of hydrogen production.
Seawater‐Based Biocatalytic Strategy: Stereoselective Reductions of Ketones with Marine Yeasts
Authors: Serra Immacolata , Guidi Benedetta , Burgaud Gaetan , Contente Martina L. , Ferraboschi Patrizia , Pinto Andrea , Compagno Concetta , Molinari Francesco , Romano Diego 
Published: September 2016

AbstractThe large consumption of freshwater in fermentations and bio‐transformations is a matter of concern for the sustainability of many bio‐processes. The use of seawater to perform bio‐processes is a sustainable alternative. In this work, we used marine yeasts from deep‐sub‐seafloor sediments grown in seawater as bio‐catalysts to perform the stereoselective reduction of different ketones, and the bio‐transformations were accomplished in seawater as well. Strains of Meyerozyma guilliermondii and Rhodotorula mucilaginosa were able to reduce different aromatic ketones with high molar conversions and moderate‐to‐high enantioselectivity with no significant differences between bio‐catalysis performed in seawater and freshwater. Finally, the selected marine yeasts were used for the reduction of key intermediates in seawater for the synthesis of molecules of pharmaceutical interest (desogestrel, norgestrel, gestodene, pramipexole).
Hydrogenation of Carbonyl Derivatives with a Well‐Defined Rhenium Precatalyst
Authors: Wei Duo , Roisnel Thierry , Darcel Christophe , Clot Eric , Sortais Jean‐Baptiste 
Published: September 2016

AbstractThe first efficient and general rhenium‐catalyzed hydrogenation of carbonyl derivatives was developed. The key to the success of the reaction was the use of a well‐defined rhenium complex bearing a tridentate diphosphinoamino ligand as the catalyst (0.5 mol %) at 70 °C in the presence of H2 (30 bar). The mechanism of the reaction was investigated by DFT(PBE0‐D3) calculations.
Nanoparticle Surface Coverage Controls the Speciation of Electrochemically Generated Chlorine
Authors: Kraikaew Pitchnaree , Tanner Eden E. L. , Sokolov Stanislav V. , Batchelor‐McAuley Christopher , Holter Jennifer , Young Neil P. , Compton Richard G. 
Published: September 2016

AbstractCyclic voltammetry is used to investigate the oxidation of chloride on platinum nanoparticles. The electrochemical response of the nanoparticles drop‐cast onto a glassy carbon electrode is compared to that recorded at a platinum macroelectrode. The use of “nano”‐ and “macro”‐scale Pt reveals different ratios of the electrochemically formed products, chlorine (Cl2) and the trichloride (Cl3−) anion. This difference in the speciation is attributed to the chloride oxidation being a surface‐reaction‐limited process. For the situation in which there are a limited number of active sites available on the electrode, owing to low nanoparticle surface coverages, the sub‐diffusion‐limited currents result in higher chloride concentrations adjacent to the electrochemical interface. This excess chloride at the interface leads to the formation of the trichloride anion. The effect of surface oxide formation towards the chloride oxidation is also examined on both electrodes. Formation of platinum oxide serves to inhibit the rate of chloride oxidation.
Formation of a Nonlinear Optical Host–Guest Hybrid Material by Tight Confinement of LDS 722 into Aluminophosphate 1D Nanochannels
Authors: Sola‐Llano Rebeca , Martínez‐Martínez Virginia , Fujita Yasuhiko , Gómez‐Hortigüela Luis , Alfayate Almudena , Uji‐i Hiroshi , Fron Eduard , Pérez‐Pariente Joaquín , López‐Arbeloa Iñigo 
Published: September 2016

AbstractIn this work, hemicyanine dye LDS 722 is encapsulated into the 1D elliptical nanochannels of MgAPO‐11 aluminophosphate by a crystallization inclusion method. The synthesis of the hybrid material has been optimized through a systematic variation of the crystallization conditions in order to obtain pure and large crystals (around 20 μm×30 μm) suitable for optical applications. The tight fitting between the molecular size of the guest dye and the pore dimensions of the host has favored a rigid planar conformation of the dye, restricting its inherent flexibility, which is confirmed by molecular simulations. Consequently, the encapsulation of LDS 722 into MgAPO‐11 has led to an astonishing enhancement of the fluorescence with respect to the dye into MgAPO‐5, with slightly larger cylindrical channels, and with respect to the dye in solution. Moreover, the perfect alignment of LDS 722 (dye with intrinsic nonlinear‐optical properties) along the channels of MgAPO‐11 has revealed attractive second‐order nonlinear properties, such as second harmonic generation, proven through microscopy measurements in single crystals.
Skeletal Rearrangement in the ZnII‐Catalyzed [4+2]‐Annulation of Disubstituted N‐Hydroxy Allenylamines with Nitrosoarenes to Yield Substituted 1,2‐Oxazinan‐3‐one Derivatives
Authors: Sharma Pankaj , Liu Rai‐Shung 
Published: September 2016

AbstractThis work reports zinc‐catalyzed [4+2]‐annulation reactions of disubstituted N‐hydroxy allenylamines with nitrosoarenes to afford substituted 1,2‐oxazinan‐3‐ones with a skeletal rearrangement. This annulation is applicable to a reasonable scope of allenylamines and nitrosoarenes. Our control experiments indicate that nitrosobenzene can also implement this annulation through a radical annulation path, but with poor efficiency. Zn(OTf)2 or AgOTf greatly improves the efficiency of this [4+2]‐annulation; the effect of these metal species is discussed in detail.
Sublimable Cationic Iridium(III) Complexes with 1,10‐Phenanthroline Derivatives as Ancillary Ligands for Highly Efficient and Polychromic Electroluminescence
Authors: Ma Dongxin , Zhang Chen , Qiu Yong , Duan Lian 
Published: September 2016

AbstractA novel series of four sublimable cationic iridium(III) complexes have been prepared with 1,10‐phenanthroline derivatives as ancillary ligands and the same negative counter‐ion, tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate, which has a large steric hindrance and widely dispersed charges, thereby increasing the ionic radii, reducing the electrostatic interaction, and thus improving the volatility. Their structural, photophysical, electrochemical, and thermal properties have been fully characterized. Upon excitation, these compounds show polychromic emission varying from green to orange in solution, which are blue‐shifted in the solid state to different extents due to π–π conjugate effects in the ancillary ligands and the resulting molecular aggregation. OLEDs fabricated by vacuum evaporation deposition demonstrated desirable device performance with high efficiency and brightness, exhibiting various electroluminescent colors dependent upon doping concentration.
A Stable Bis(benzocyclobutadiene)‐Annelated Tetraazapentacene Derivative
Authors: Biegger Philipp , Schaffroth Manuel , Tverskoy Olena , Rominger Frank , Bunz Uwe H. F. 
Published: September 2016

AbstractBiphenylene‐2,3‐dione is a powerful reagent to build up cyclobutadiene‐containing azapolyheterocycles. The target structures are formed in high yields through classical condensation of suitable aromatic diamines with the biphenylenedione. To achieve the title compound, the biphenylenedione is coupled with a diaminobenzothiadiazole derivative. Reductive cleavage of the thiadiazole ring and subsequent condensation with the biphenylenedione gives the title compound in which a central tetraazapentacene is flanked by two benzocyclobutadiene units. This compound is stable despite its extended π‐system and its optical features are blueshifted in comparison to those of the symmetrical tetraazapentacene.
Radical Reactions Induced by Visible Light in Dichloromethane Solutions of Hünig's Base: Synthetic Applications and Mechanistic Observations
Authors: Böhm Alexander , Bach Thorsten 
Published: September 2016

Abstractβ‐(3‐Iodopropoxy)‐substituted α,β‐unsaturated lactams, lactones, and cycloalkenones (eight examples) underwent reductive radical reactions in a dichloromethane solution of N,N‐diisopropylethylamine (Hünig's base) upon irradiation with visible light (λ=419 nm). Apart from plain reduction reactions (hydro‐de‐iodination), a significant degree of cyclization was observed in three cases. In parallel to the conversion of the substrates, the formation of intensely colored by‐products was observed. Based on mass spectrometric evidence and upon comparison with known compounds, the by‐products were identified as cyanine dyes. Their formation supports the hypothesis that irradiation of dichloromethane solutions of Hünig's base leads to the formation of radicals, which in turn can either initiate a radical reaction or combine with cyanine precursors. It was shown by deuterium‐labelling experiments, that one equivalent of dichloromethane is incorporated into the cyanine dyes and that the reductive quenching of radical intermediates is at least partially due to hydrogen abstraction from the solvent. As a consequence, a reductive cyclization of the starting materials is favored in CD2Cl2 solutions as shown for two β‐(3‐iodopropoxy)‐substituted tetronates, which underwent in dichloromethane almost exclusive reduction, but gave predominantly the cyclization products in CD2Cl2.
The Evolution of the Total Synthesis of Rocaglamide
Authors: Zhou Zhe , Dixon Darryl D. , Jolit Anais , Tius Marcus A. 
Published: September 2016

AbstractThe complex flavagline, (−)‐rocaglamide, possesses a synthetically intriguing tricyclic scaffold with five contiguous stereocenters and also exhibits potent anticancer, anti‐inflammatory and insecticidal activity. This full account details distinct approaches to (±)‐ and (−)‐rocaglamide utilizing Brønsted acid catalyzed and asymmetric Pd0‐catalyzed Nazarov chemistry developed in our laboratory, respectively. The successful asymmetric synthesis revealed unforeseen mechanistic complexity that required adjusting our strategy to overcome an unanticipated racemization process, an unusual reversible ring‐cleavage step and a very facile trialkylsilyl group migration.