bluuebunny/crossref_metadata_2025 huggingface dataset:
Solution Layer Deposition: A Technique for the Growth of Ultra‐Pure Manganese Oxides on Silica at Room Temperature
Authors: Cure Jérémy , Piettre Kilian , Coppel Yannick , Beche Eric , Esvan Jérôme , Collière Vincent , Chaudret Bruno , Fau Pierre
Published: January 2016

With the ever increasing miniaturization in microelectronic devices, new deposition techniques are required to form high‐purity metal oxide layers. Herein, we report a liquid route to specifically produce thin and conformal amorphous manganese oxide layers on silicon substrate, which can be transformed into a manganese silicate layer. The undesired insertion of carbon into the functional layers is avoided through a solution metal–organic chemistry approach named Solution Layer Deposition (SLD). The growth of a pure manganese oxide film by SLD takes place through the decoordination of ligands from a metal–organic complex in mild conditions, and coordination of the resulting metal atoms on a silica surface. The mechanism of this chemical liquid route has been elucidated by solid‐state 29Si MAS NMR, XPS, SIMS, and HRTEM.
Giant Amplification of Photoswitching by a Few Photons in Fluorescent Photochromic Organic Nanoparticles
Authors: Su Jia , Fukaminato Tuyoshi , Placial Jean‐Pierre , Onodera Tsunenobu , Suzuki Ryuju , Oikawa Hidetoshi , Brosseau Arnaud , Brisset François , Pansu Robert , Nakatani Keitaro , Métivier Rémi
Published: January 2016

Controlling or switching the optical signal from a large collection of molecules with the minimum of photons represents an extremely attractive concept. Promising fundamental and practical applications may be derived from such a photon‐saving principle. With this aim in mind, we have prepared fluorescent photochromic organic nanoparticles (NPs), showing bright red emission, complete ON–OFF contrast with full reversibility, and excellent fatigue resistance. Most interestingly, upon successive UV and visible light irradiation, the NPs exhibit a complete fluorescence quenching and recovery at very low photochromic conversion levels (<5 %), leading to the fluorescence photoswitching of 420±20 molecules for only one converted photochromic molecule. This “giant amplification of fluorescence photoswitching” originates from efficient intermolecular energy‐transfer processes within the NPs.
Der größte metalloide Cluster der 14. Gruppe, Ge18[Si(SiMe3)3]6: eine Zwischenstufe auf dem Weg zu elementarem Germanium
Authors: Kysliak Oleksandr , Schrenk Claudio , Schnepf Andreas
Published: January 2016

Die Oxidation von [Ge9(Hyp)3]− (Hyp=Si(SiMe3)3) mit einem FeII‐Salz ergibt den größten metalloiden Cluster der 14. Gruppe, Ge18(Hyp)6 (1). Die Anordnung der 18 Germaniumatome in 1 zeigt dabei Ähnlichkeiten zur Festkörpermodifikation Ge(cF136). Zusätzlich kann 1 als makropolyedrischer Cluster zweier Ge9‐Einheiten aufgefasst werden. Quantenchemische Rechnungen weisen auf ein gespanntes System hin, sodass 1 als eine erste abgefangene Zwischenstufe, ausgehend von Ge9‐Einheiten, hin zu elementarem Germanium in der Clathrat(II)‐Struktur Ge(cF136), aufgefasst werden kann.
Macrocyclic Transformations from Norrole to Isonorrole and an N‐Confused Corrole with a Fused Hexacyclic Ring System Triggered by a Pyrrole Substituent
Authors: Li Miao , Wei Pingchun , Ishida Masatoshi , Li Xin , Savage Mathew , Guo Rui , Ou Zhongping , Yang Sihai , Furuta Hiroyuki , Xie Yongshu
Published: January 2016

Three kinds of fused porphyrinoids, L2–L4, possessing different types of corrole‐based frameworks were synthesized from a pyrrole‐substituted corrole isomer (norrole L1). Oxidation of L1 afforded a unique N‐Cmeso‐fused pyrrolyl isonorrole L2, involving the fusion of an auxiliary pyrrolic NH moiety with a meso‐sp3‐hybridized carbon atom. Subsequently, L2 underwent macrocycle transformations to give singly and doubly N‐CAr‐fused N‐confused corroles, L3 and L4, respectively. L3 and L4 contain fused [5.7.6.5]‐tetra‐ and [5.6.7.7.6.5]‐hexacyclic structures, respectively, prepared through lateral annulation. These skeletal transformation reactions from norrole to its isomer isonorrole and finally to N‐confused corrole indicate that multiply fused porphyrinoids could be readily synthesized from pyrrole‐appended confused porphyrinoids.
Layered Black Phosphorus: Strongly Anisotropic Magnetic, Electronic, and Electron‐Transfer Properties
Authors: Sofer Zdeněk , Sedmidubský David , Huber Štěpán , Luxa Jan , Bouša Daniel , Boothroyd Chris , Pumera Martin
Published: January 2016

Layered elemental materials, such as black phosphorus, exhibit unique properties originating from their highly anisotropic layered structure. The results presented herein demonstrate an anomalous anisotropy for the electrical, magnetic, and electrochemical properties of black phosphorus. It is shown that heterogeneous electron transfer from black phosphorus to outer‐ and inner‐sphere molecular probes is highly anisotropic. The electron‐transfer rates differ at the basal and edge planes. These unusual properties were interpreted by means of calculations, manifesting the metallic character of the edge planes as compared to the semiconducting properties of the basal plane. This indicates that black phosphorus belongs to a group of materials known as topological insulators. Consequently, these effects render the magnetic properties highly anisotropic, as both diamagnetic and paramagnetic behavior can be observed depending on the orientation in the magnetic field.
Influence of Equatorial CH⋅⋅⋅O Interactions on Secondary Kinetic Isotope Effects for Methyl Transfer
Authors: Wilson Philippe B. , Williams Ian H.
Published: January 2016

DFT calculations for methyl cation complexed within a constrained cage of water molecules permit the controlled manipulation of the “axial” donor/acceptor distance and the “equatorial” distance to hydrogen‐bond acceptors. The kinetic isotope effect k(CH3)/k(CT3) for methyl transfer within a cage with a short axial distance becomes less inverse for shorter equatorial C⋅⋅⋅O distances: a decrease of 0.5 Å results in a 3 % increase at 298 K. Kinetic isotope effects in AdoMet‐dependent methyltransferases may be m∧odulated by CH⋅⋅⋅O hydrogen bonding, and factors other than axial compression may contribute, at least partially, to recently reported isotope‐effect variations for catechol‐O‐methyltransferase and its mutant structures.
Directly Diphenylborane‐Fused Porphyrins
Authors: Fujimoto Keisuke , Oh Juwon , Yorimitsu Hideki , Kim Dongho , Osuka Atsuhiro
Published: January 2016

Mono‐ and bis(diphenylborane)‐fused porphyrins were synthesized from the corresponding β‐(2‐trimethylsilylphenyl)‐substituted porphyrins through the sequence of Si–B exchange reaction, intramolecular bora‐Friedel–Crafts reaction, and ring‐closing Si–B exchange reaction. Effective electronic interactions of the empty p‐orbital of the boron atom with the porphyrin π‐circuit lead to red‐shifted absorption spectra and substantially decreased LUMO energy levels. Pyridine adds at the boron center to cause disruption of the electronic interaction of the boron atom with large association constants (1.9–17×104 m−1) depending on the central metal at the porphyrin. The ZnII complex behaved as a hetero‐dinuclear Lewis acid, exhibiting regioselective binding of pyridines at the boron or the zinc center.
Syntheses and Promising Properties of Dense Energetic 5,5′‐Dinitramino‐3,3′‐azo‐1,2,4‐oxadiazole and Its Salts
Authors: Tang Yongxing , Gao Haixiang , Mitchell Lauren A. , Parrish Damon A. , Shreeve Jean'ne M.
Published: January 2016

A planar energetic molecule with high density, 5,5′‐dinitramino‐3,3′‐azo‐1,2,4‐oxadiazole (4), was obtained by the nitration of 5,5′‐diamino‐3,3′‐azo‐1,2,4‐oxadiazole using 100 % nitric acid. In addition, selected nitrogen‐rich salts were prepared. Of them, the neutral compound 4 and its hydroxylammonium salt, 6, were further confirmed by single‐crystal X‐ray diffraction. Physicochemical and energetic properties including density, thermal stability, and sensitivity were investigated. The energetic performance from the calculated heats of formation and experimental densities indicates that many of them have potential applications as energetic materials.
Mussel‐Directed Synthesis of Nitrogen‐Doped Anatase TiO2
Authors: Xie Jingjing , Xie Hao , Su Bao‐Lian , Cheng Yi‐bing , Du Xiaodong , Zeng Hui , Wang Menghu , Wang Weimin , Wang Hao , Fu Zhengyi
Published: January 2016

Structure‐forming processes leading to biominerals are well worth learning in pursuit of new synthetic techniques. Strategies that attempt to mimic nature in vitro cannot replace an entire complex natural organism, requiring ingenuity beyond chemists′ hands. A “bioprocess‐inspired synthesis” is demonstrated for fabrication of N‐doped TiO2 materials at ambient temperature by direct implantation of precursor into living mussels. The amorphous precursor transforms into N‐doped anatase TiO2 with a hierarchical nanostructure. Synthetic TiO2 exhibits high phase stability and enhanced visible‐light photocatalytic activity as a result of modifications to its band gap during in vivo mineralization. Intracellular proteins were found to be involved in TiO2 mineralization. Our findings may inspire material production by new synthetic techniques, especially under environmentally benign conditions.
Hydroxylation versus Halogenation of Aliphatic C−H Bonds by a Dioxygen‐Derived Iron–Oxygen Oxidant: Functional Mimicking of Iron Halogenases
Authors: Chatterjee Sayanti , Paine Tapan Kanti
Published: January 2016

An iron–oxygen intermediate species generated in situ in the reductive activation of dioxygen by an iron(II)–benzilate complex of a monoanionic facial N3 ligand, promoted the halogenation of aliphatic C−H bonds in the presence of a protic acid and a halide anion. An electrophilic iron(IV)–oxo oxidant with a coordinated halide is proposed as the active oxidant. The halogenation reaction with dioxygen and the iron complex mimics the activity of non‐heme iron halogenases.
A Cobalt(I) Pincer Complex with an η2‐Caryl−H Agostic Bond: Facile C−H Bond Cleavage through Deprotonation, Radical Abstraction, and Oxidative Addition
Authors: Murugesan Sathiyamoorthy , Stöger Berthold , Pittenauer Ernst , Allmaier Günter , Veiros Luis F. , Kirchner Karl
Published: January 2016

The synthesis and reactivity of a CoI pincer complex [Co(ϰ3P,CH,P‐P(CH)PNMe‐iPr)(CO)2]+ featuring an η2‐ Caryl−H agostic bond is described. This complex was obtained by protonation of the CoI complex [Co(PCPNMe‐iPr)(CO)2]. The CoIII hydride complex [Co(PCPNMe‐iPr)(CNtBu)2(H)]+ was obtained upon protonation of [Co(PCPNMe‐iPr)(CNtBu)2]. Three ways to cleave the agostic C−H bond are presented. First, owing to the acidity of the agostic proton, treatment with pyridine results in facile deprotonation (C−H bond cleavage) and reformation of [Co(PCPNMe‐iPr)(CO)2]. Second, C−H bond cleavage is achieved upon exposure of [Co(ϰ3P,CH,P‐P(CH)PNMe‐iPr)(CO)2]+ to oxygen or TEMPO to yield the paramagnetic CoII PCP complex [Co(PCPNMe‐iPr)(CO)2]+. Finally, replacement of one CO ligand in [Co(ϰ3P,CH,P‐P(CH)PNMe‐iPr)(CO)2]+ by CNtBu promotes the rapid oxidative addition of the agostic η2‐Caryl−H bond to give two isomeric hydride complexes of the type [Co(PCPNMe‐iPr)(CNtBu)(CO)(H)]+.
Multicomponent Diene‐Transmissive Diels–Alder Sequences Featuring Aminodendralenes
Authors: Tan Siu Min , Willis Anthony C. , Paddon‐Row Michael N. , Sherburn Michael S.
Published: January 2016

1‐Aminodecalins were prepared from acyclic precursors by combining the powerful twofold diene‐transmissive Diels–Alder chemistry of [3]dendralenes with the simplicity of enamine formation. On mixing at ambient temperature, a simple dienal condenses with a primary or secondary amine to generate the enamine, a 1‐amino‐[3]dendralene in situ, and this participates as a double diene in a sequence of two Diels–Alder events with separate dienophiles. Overall, four C−C bonds and one C−N bond are formed. Mechanistic insights into these reactions are provided by means of density functional theory calculations.
A Triatomic Silicon(0) Cluster Stabilized by a Cyclic Alkyl(amino) Carbene
Authors: Mondal Kartik Chandra , Roy Sudipta , Dittrich Birger , Andrada Diego M. , Frenking Gernot , Roesky Herbert W.
Published: January 2016

Reduction of the neutral carbene tetrachlorosilane adduct (cAAC)SiCl4 (cAAC=cyclic alkyl(amino) carbene :C(CMe2)2(CH2)N(2,6‐iPr2C6H3) with potassium graphite produces stable (cAAC)3Si3, a carbene‐stabilized triatomic silicon(0) molecule. The Si−Si bond lengths in (cAAC)3Si3 are 2.399(8), 2.369(8) and 2.398(8) Å, which are in the range of Si−Si single bonds. Each trigonal pyramidal silicon atom of the triangular molecule (cAAC)3Si3 possesses a lone pair of electrons. Its bonding, stability, and electron density distributions were studied by quantum chemical calculations.
Visible‐Light‐Promoted Photocatalytic B−C Coupling via a Boron‐Centered Carboranyl Radical: Facile Synthesis of B(3)‐Arylated o‐Carboranes
Authors: Zhao Da , Xie Zuowei
Published: January 2016

A visible‐light‐mediated in situ generation of a boron‐centered carboranyl radical (o‐C2B10H11.) has been described. With eosin Y as a photoredox catalyst, 3‐diazonium‐o‐carborane tetrafluoroborate [3‐N2‐o‐C2B10H11][BF4] was converted into the corresponding boron‐centered carboranyl radical intermediate, which can undergo efficient electrophilic substitution reaction with a wide range of (hetero)arenes. This general and simple procedure provides a metal‐free alternative for the synthesis of 3‐(hetero)arylated‐o‐carboranes.
Hydrogen Bonds Dictate the Coordination Geometry of Copper: Characterization of a Square‐Planar Copper(I) Complex
Authors: Dahl Eric W. , Szymczak Nathaniel K.
Published: January 2016

6,6′′‐Bis(2,4,6‐trimethylanilido)terpyridine (H2TpyNMes) was prepared as a rigid, tridentate pincer ligand containing pendent anilines as hydrogen bond donor groups in the secondary coordination sphere. The coordination geometry of (H2TpyNMes)copper(I)‐halide (Cl, Br and I) complexes is dictated by the strength of the NH–halide hydrogen bond. The CuICl and CuIICl complexes are nearly isostructural, the former presenting a highly unusual square‐planar geometry about CuI. The geometric constraints provided by secondary interactions are reminiscent of blue copper proteins where a constrained geometry, or entatic state, allows for extremely rapid CuI/CuII electron‐transfer self‐exchange rates. Cu(H2TpyNMes)Cl shows similar fast electron transfer (≈105 m−1 s−1) which is the same order of magnitude as biological systems.
Sensitive amperometric pyridoxine sensor based on self‐assembled Prussian blue nanoparticle‐modified poly(o‐phenylenediamine)/glassy carbon electrode
Authors: Ojani Reza , Hamidi Parisa , Raoof Jahan‐Bakhsh
Published: February 2016

Prussian blue nanoparticles (PBNPs) were prepared by a self‐assembly process on a glassy carbon electrode (GCE) modified with poly(o‐phenylenediamine) (PoPD) film. The stepwise fabrication process of PBNP‐modified PoPD/GCE was characterized using scanning electron microscopy and electrochemical impedance spectroscopy. The prepared PBNPs showed an average size of 70 nm and a homogeneous distribution on the surface of the modified electrode. The PBNPs/PoPD/GCE showed electrocatalytic activity towards the oxidation of pyridoxine (PN) and was used as an amperometric sensor. The modified electrode exhibited a linear response for PN oxidation over the concentration range 3–38.5 μM with a detection limit of ca 6.10 × 10−7 M (S/N = 3) and sensitivity of 2.79936 × 103 mA M−1 cm−2 using an amperometric method. The mechanism and kinetics of the catalytic oxidation reaction of PN were investigated using cyclic voltammetry and chronoamperometry. The values of α, kcat and D were estimated as 0.36, 1.089 × 102 M−1 s−1 and 8.9 × 10−5 cm2 s−1, respectively. This sensor also exhibited good anti‐interference and selectivity. Copyright © 2016 John Wiley & Sons, Ltd.
In situ fast polymerization of graphene nanosheets‐filled poly(methyl methacrylate) nanocomposites
Authors: Zhang Lan‐Ying , Zhang Yang‐Fei
Published: January 2016

A series of graphene nanosheets‐filled poly(methyl methacrylate) nanocomposites (GNS/PMMA) is successfully prepared by an in situ fast polymerization method with graphene weight fractions from 0.1 to 2.0 wt %. In situ polymerization is effective in well dispersing of GNS in matrixes and suitable for both low and high content of GNS. The synthesis processes of polymer composites could be simplified and fast by using industrial grade graphene. The GNS fillers are found to disperse homogeneously in the PMMA matrix. The maximum electrical conductivity of the composites achieves 0.57 S m−1, with an extremely low percolation threshold of 0.3 wt %. The electrical conductivities are further predicted by percolation theory and found to agree well with the experimental results. The results indicate that the microstructures, thermal, electrical, and mechanical properties of PMMA polymer are significantly improved by adding a low amount of graphene nanosheets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43423.
Die Verwendung von Gelenken im Massivbrückenbau
Authors: Veihelmann Karen , Holzer Stefan M.
Published: February 2016

Die Beurteilung historischer Brücken gewinnt für heutige Ingenieure immer mehr an Wichtigkeit. Oftmals fehlen jedoch die dafür notwendigen Kriterien. Im vorliegenden Artikel wird die Geschichte des Dreigelenkbogens im Massivbrückenbau dargestellt: Während Gelenke im Eisenbau bereits seit den 1860er‐Jahren verwendet wurden, wurden diese im Massivbrückenbau erst deutlich später eingeführt (in Deutschland ab 1880). Zum Ende des 19. Jahrhunderts wurde die Konstruktion mit Gelenken in Deutschland jedoch für größere Brücken zur Standardbauweise. Gründe für den Aufschwung des Dreigelenkbogens bei Massivbrücken waren auf der einen Seite die Vermeidung von Rissen, auf der anderen Seite die Vereinfachung der Berechnung des nunmehr statisch bestimmten Systems. Beginnend mit den ersten Ideen von JULES DUPUIT (1870) und FRIEDRICH HEINZERLING (1872) wird die wissenschaftliche Seite ebenso beleuchtet wie der praktische Einsatz von Gelenken. Die verschiedenen Bauarten früher Gelenke sowie deren Vor‐ und Nachteile werden erläutert, um dem modernen Ingenieur ein Werkzeug zur Hand zu geben, das die heutige Beurteilung einer solchen Brücke erleichtert.

Hinges in historic concrete and masonry arches. On the history of the three‐hinged arch

The three‐hinged arch, while increasingly common in steel bridge construction from the 1860ies, was introduced more reluctantly into masonry and concrete bridge building. However, by the end of the 19th century, it had found widespread application, particularly in Germany. Considerations of crack prevention as well as ease and consistency of the mechanical modelling of masonry arches were evidently the driving forces behind this development. The present paper describes the history of the hinged vaulted bridge, from the first suggestions by the eminent French engineer JULES DUPUIT (published in 1870) up to the early years of the 20th century. Particular attention is given to temporary and “imperfect” hinges which may be neither visible nor active in the finished state of the bridge, and to the historic development and design of permanent hinges, outlining the range of constructive solutions the modern engineer may encounter when assessing the state of a late 19th century vaulted bridge.
Einheitliches Querkraftmodell zur Bemessung von Stahl‐ und Spannbetonbrücken im Bestand
Authors: Herbrand Martin , Kueres Dominik , Claßen Martin , Hegger Josef
Published: February 2016

Während das Biegetragverhalten von Betonbauteilen sehr genau beschrieben werden kann, ist das Querkrafttragverhalten schubschlanker Bauteile noch immer Gegenstand kontroverser Diskussionen. Für die Bemessungspraxis sind Modelle notwendig, die einfach anwendbar sind und dennoch ausreichend genaue und damit wirtschaftliche Vorhersagen erlauben. Das hier gezeigte einheitliche Querkraftmodell ermöglicht bei der Bemessung einen stetigen Übergang zwischen Bauteilen ohne und mit Querkraftbewehrung. Der Vergleich mit den ACI‐DAfStb‐Querkraftdatenbanken belegt, dass das vorgeschlagene Modell für Bauteile mit Querkraftbewehrung zu deutlich geringeren Streuungen und gleichzeitig einem besseren Sicherheitsniveau im Vergleich zum aktuellen EC2 führt. Insbesondere für Bauteile mit geringen Querkraftbewehrungsgraden ergeben sich hierdurch höhere Tragfähigkeiten, was z.B. für die Nachrechnung von Bestandsbauwerken wie Brücken von Vorteil ist. Die beispielhafte Nachrechnung einer Bestandsbrücke bestätigt die deutliche Steigerung der rechnerischen Querkrafttragfähigkeit für Spannbetonbrücken mit geringen Querkraftbewehrungsgraden.

Uniform Shear Design Method for Existing Reinforced and Prestressed Concrete Briges

While the flexural bending behavior of concrete structures can be described accurately, the shear behavior of slender beams still is subject of controversial discussions. For design praxis, easy to use and at the same time precise models are necessary to ensure economical design. The proposed uniform shear design procedure provides a continuous transition between beams without and with shear reinforcement. The comparison with the shear databanks of the ACI‐DAfStb confirms that the proposed model provides a strongly reduced coefficient of variation as well as a higher degree of safety in comparison to the current model of EC2. Especially for beams with small amounts of shear reinforcement, higher shear capacities result which is beneficiary for the recalculation of existing structures like bridges. The exemplary recalculation of an existing bridge confirms a notable increase of the shear capacity for prestressed concrete bridges with small amounts of shear reinforcement.
Effects of progesterone on hyperoxia‐induced damage in mouse C8‐D1A astrocytes
Authors: Weber Friederike , Endesfelder Stefanie , Bührer Christoph , Berns Monika
Published: February 2016

Introduction

The birth of most mammals features a dramatic increase in oxygen while placenta‐derived hormones such as β‐estradiol and progesterone plummet. In experimental newborn animals, transiently elevated oxygen concentrations cause death of neurons, astrocytes, and oligodendrocyte precursors. High oxygen has been associated with cerebral palsy in human preterm infants while progesterone is being used to prevent preterm delivery and investigated as a neuroprotective agent.

Methods

In this study, we investigated the effects of hyperoxia (80% O2 for 24, 48, and 72 h) on cultured C8‐D1A astrocytes in the presence or absence of progesterone at concentrations ranging from 10−9 to 10−5 mol/L.

Results

Hyperoxia measured by methytetrazolium assay (MTT) reduced cell viability, increased release of lactate dehydrogenase (LDH), reduced carboxyfluorescein diacetate succinimidyl ester (CFSE)‐assessed cell proliferation, and downregulated Cylin D2 expression. Progesterone did not affect any of these hyperoxia‐mediated indicators of cell death or malfunctioning. Real‐time PCR analysis showed that hyperoxia caused downregulation of the progesterone receptors PR‐AB und PR‐B.

Conclusions

Our experiments showed that there was no protective effect of progesterone on hyperoxia‐inducted cell damage on mouse C8‐D1A astrocytes. Down regulation of the progesterone receptors might be linked to the lack of protective effects.
High‐risk older smokers' perceptions, attitudes, and beliefs about lung cancer screening
Authors: Cataldo Janine K.
Published: January 2016

The US Preventive Services Task Force recommends that smokers aged 55–80 should be screened annually with low‐dose computed tomography (LDCT). This study identified demographics, smoking history, health risk perceptions, knowledge, and attitudes factors of older smokers (≥55 years) related to LDCT agreement. Using binary logistic regression, a predictive model of factors to explain LDCT agreement was produced. This is a cross‐sectional, national, online survey of 338 older smokers (≥55 years) with a ≥30 pack‐year smoking history. Over 82% of the sample believed that a person who continues to smoke after the age of 40 has at least a 25% chance of developing lung cancer and 77.3% would “agree to a LDCT today”. Using chi‐square analyses, six variables that were significant at the 0.10 level were selected for inclusion in model development. Four of the independent variables made a unique statistically significant contribution to the model: perceives accuracy of the LDCT as an important factor in the decision to have a LDCT scan; believes that early detection of LC will result in a good prognosis; believes that they are at high risk for lung cancer; and is not afraid of CT scans. Of note, only 10.9% believed that a negative CT scan result would mean that they could continue to smoke. Older smokers are aware of the risks of smoking, are interested in smoking cessation, and most are interested in and positive about LDCT. Cognitive aspects of participation in screening are key to increasing the uptake of lung cancer screening among high‐risk smokers.
Prognostic impact of the residual SYNTAX score on in‐hospital outcomes in patients undergoing primary percutaneous coronary intervention
Authors: Khan Razi , Al‐Hawwas Malek , Hatem Raja , Azzalini Lorenzo , Fortier Annik , Joliecoeur E. Marc , Tanguay Jean‐Francois , Lavoie‐L'Allier Philippe , Ly Hung Q.
Published: February 2016

Objectives

This study sought to assess the impact of residual coronary artery disease (CAD), using the residual SYNTAX score (rSS), on in‐hospital outcomes after primary percutaneous intervention (PPCI). The study also aimed to determine independent predictors for high rSS. Residual CAD has been associated with worsened prognosis in patients undergoing PCI for non‐ST acute coronary syndromes. The rSS is a systematic angiographic score that measures the extent and complexity of residual CAD after PCI.

Materials and Methods

Data from 243 consecutive patients undergoing PPCI for ST‐elevation myocardial infarction (STEMI) were analyzed. The rSS was derived from post‐PPCI angiography. Patients were dichotomized into low (<8) and high rSS (≥8) groups and outcomes were compared between groups. The primary outcome of net adverse cardiovascular events (NACE) consisted of a composite of in‐hospital death, congestive heart failure (CHF), recurrent MI and bleeding.

Results

The mean rSS was 4.7 (±7.2). A high rSS was associated with the primary outcome (P < 0.0001), in‐hospital death (P = 0.0026), periprocedural death (P < 0.0001), CHF (P < 0.0004) and acute kidney injury (P < 0.0019). A high rSS was also an independent predictor of the primary outcome with an OR of 3.82. Independent predictors of a high rSS included a history of diabetes (OR 2.8), previous MI (OR 5.75), 2‐vessel disease (VD) (OR 15.48, vs. 1‐VD) and 3‐VD (OR 57.06, vs. 1‐VD).

Conclusions

Residual CAD, as assessed by the rSS, confers a worsened prognosis in patients undergoing PPCI. Diabetes, previous MI and multi‐vessel disease were independent predictors of a high rSS. © 2016 Wiley Periodicals, Inc.
Carlino to the rescue: Use of intralesion contrast injection for bailout antegrade and retrograde crossing of complex chronic total occlusions
Authors: Amsavelu Suwetha , Carlino Mauro , Brilakis Emmanouil S.
Published: February 2016

Percutaneous coronary intervention (PCI) of coronary chronic total occlusions (CTO) can be challenging. Although several crossing techniques are available, in some cases their application fails to cross the occlusion. Carlino et al. have pioneered the technique of hydraulic microdissection by contrast injection through a microcatheter inserted into the lesion. We report two CTO PCI cases in which the use of the Carlino technique enabled success after other crossing strategies failed to cross the occlusion. © 2016 Wiley Periodicals, Inc.
Photocatalytic Activity Evolution of Different Morphological TiO2 Shells on Ag Nanowires
Authors: Jia Changchao , Yang Ping , Li Jia , Huang Baibiao , Matras‐Postolek Katarzyna
Published: January 2016

Ag nanowire@TiO2 (Ag NW@TiO2) heterostructures with core–shell, necklace‐like, and particle‐decorated morphologies were fabricated to investigate the evolution of the photocatalytic properties. The deposition of the TiO2 phase on the surface of the Ag NWs was achieved through a solvothermal method. Thioglycolic acid (TGA) not only solves the tricky issue of substantial lattice mismatch between the Ag NW core and TiO2 shell, but also plays an important role in precisely controlling how the TiO2 is coated on the Ag NW surface. H2O molecules affect the deposition of the TiO2 phase on the Ag NWs. The photocatalytic activity of the Ag NW@TiO2 heterostructures with different morphologies was evaluated by degradation of methyl orange. The molar ratio of TiO2 to Ag is crucial for the photocatalytic activity, and the Ag NW@TiO2 sample with core–shell structure exhibits an excellent performance compared with the others, owing to the TiO2 phase being densely attached to the Ag NW surface, which forms a well‐developed combined interface.
Arylmalonate Decarboxylase‐Catalyzed Asymmetric Synthesis of Both Enantiomers of Optically Pure Flurbiprofen
Authors: Gaßmeyer Sarah Katharina , Wetzig Jasmin , Mügge Carolin , Assmann Miriam , Enoki Junichi , Hilterhaus Lutz , Zuhse Ralf , Miyamoto Kenji , Liese Andreas , Kourist Robert
Published: January 2016

The bacterial decarboxylase (AMDase) catalyzes the enantioselective decarboxylation of prochiral arylmalonates with high enantioselectivity. Although this reaction would provide a highly sustainable synthesis of active pharmaceutical compounds such as flurbiprofen or naproxen, competing spontaneous decarboxylation has so far prevented the catalytic application of AMDase. Here, we report on reaction engineering and an alternate protection group strategy for the synthesis of these compounds that successfully suppresses the side reaction and provides pure arylmalonic acids for subsequent enzymatic conversion. Protein engineering increased the activity of the synthesis of the (S)‐ and (R)‐enantiomers of flurbiprofen. These results demonstrated the importance of synergistic effects in the optimization of this decarboxylase. The asymmetric synthesis of both enantiomers in high optical purity (>99 %) and yield (>90 %) can be easily integrated into existing industrial syntheses of flurbiprofen, thus providing a sustainable method for the production of this important pharmaceutical ingredient.
Probing the Structural Changes and Redox Behavior of Mixed Molybdate Catalysts under Ammoxidation Conditions: An Operando Raman Spectroscopy Study
Authors: Engeldinger Jana , Radnik Jörg , Kreyenschulte Carsten , Devred François , Gaigneaux Eric M. , Fischer Achim , Zanthoff Horst‐Werner , Bentrup Ursula
Published: January 2016

Mixed model molybdate catalysts that contain CoMoO4, Bi2Mo3O12, and Fe2Mo3O12 were investigated in the ammoxidation reaction of propene to acrylonitrile to study the redox behavior of the iron molybdate component. The flexible changes of the oxidation state of the Fe component during ammoxidation were followed by examining the intensity changes of the characteristic bands of Fe2Mo3O12 and FeMoO4 in the Raman spectra and could be correlated with the catalyst performance examined by simultaneous MS analysis. Depending on the catalyst composition and the oxygen content in the feed, Fe2Mo3O12 is reduced to a different extent, and consequently, FeMoO4 is formed, which is accompanied by a restructuring of the catalyst and the formation of nanostructured MoOx species. In accordance with previous investigations, operando Raman studies revealed that CoMoO4 and Bi2Mo3O12 influence the redox behavior of Fe2Mo3O12 in different ways.
Base‐Catalyzed One‐Pot Synthesis of Unsymmetrical Fluorenes from Aromatic ortho‐Dialdehydes and 1,3‐Dicarbonyl Compounds
Authors: Seo Ue Ryung , Chung Young Keun , Lee Chulbom
Published: January 2016

A synthetic route for the preparation of unsymmetrically polysubstituted fluorenes was developed through the base‐catalyzed one‐pot domino reactions of aromatic ortho‐dialdehydes with 1,3‐dicarbonyl compounds. This protocol provides expeditious access to indene‐fused polycyclic aromatic hydrocarbons such as the benzo[b]fluorene and 13H‐indeno[1,2‐b]anthracene skeletons.
Chemical Surface Characterization of Activated Carbons by Adsorption Excess of Probe Molecules
Authors: Treese Julian , Pasel Christoph , Luckas Michael , Bathen Dieter
Published: January 2016

Activated carbons are one of the most common industrial adsorbents in liquid‐phase applications. It is known that the surface groups of the activated carbon can have a significant influence on the adsorption process from the liquid phase. Therefore, it is desirable to measure surface groups on activated carbons. This opens up the possibility to use group‐contribution methods to model and predict adsorption isotherms. An idea is presented to characterize the inner surface of activated carbons by three types of surface groups: aromatic, polar, and nonpolar surface groups. The amounts of these surface groups were calculated from excess adsorption isotherms of probe molecules on ten activated carbons. This lays the groundwork for further simulation studies of liquid‐phase adsorption using group‐contribution methods.
Cellular Response to Cu‐ and Zn‐Induced Oxidative Stress in Aspergillus fumigatus Isolated From Polluted Soils in Bulgaria
Authors: Krumova Ekaterina , Kostadinova Nedelina , Miteva‐Staleva Jeny , Gryshko Vitalii , Angelova Maria
Published: February 2016

The fungal strain Aspergillus fumigatus 32 isolated from the tailings pond at the copper mine “Vlaykov vruh,” Bulgaria, showed high tolerance to Cu2+ and Zn2+. This study was designed to explore the relationship between Cu2+ and Zn2+ tolerance and cellular response to oxidative stress. The model strain was identified to species level by morphological and molecular methods. Fungal cultures were exposed to enhanced concentrations of metal ions. The effect of Cu2+ and Zn2+ was evaluated by the changes in fungal growth and morphology, the level of oxidative stress biomarkers, and the antioxidant activities of enzymes such as superoxide dismutase (SOD) and catalase (CAT). Two different cellular responses occurred: The concentrations of up to 500 μg/mL caused enhanced levels of oxidative stress biomarkers (glycogen and trehalose accumulation and oxidatively damaged protein content), as well as an increase in SOD and CAT activities. The treatment with concentrations from 500 to 2000 μg/mL led to enhanced glycogen consumption, accelerated proteolysis, and a decrease in SOD and CAT activities. The present results provide additional information about the participation of oxidative stress and antioxidant defense in enhanced tolerance of fungi isolated from metal‐polluted soils. Probably, survival at extremely high concentrations also requires the participation of other defense mechanisms. Furthermore, the enhanced understanding of these processes will provide essential tools for efficient remediation practices.
Patient‐reported outcomes, body composition, and nutrition status in patients with head and neck cancer: Results from an exploratory randomized controlled exercise trial
Authors: Capozzi Lauren C. , McNeely Margaret L. , Lau Harold Y. , Reimer Raylene A. , Giese‐Davis Janine , Fung Tak S. , Culos‐Reed S. Nicole
Published: February 2016

BACKGROUND

Patients with head and neck cancer experience loss of weight and muscle mass, decreased functioning, malnutrition, depression, and declines in quality of life during and after treatment. The purpose of this exploratory randomized study was to determine the optimal timing for the initiation of a lifestyle and progressive resistance exercise training intervention (during or after radiation therapy), as determined by intervention adherence and by comparing between‐group outcomes across 24 weeks.

METHODS

Sixty patients with head and neck cancer were randomized to engage in a 12‐week lifestyle intervention and progressive resistance‐training program either during radiation treatment or immediately after completion. The primary outcome of body composition—specifically, lean body mass, body mass index, and body fat—as well as secondary outcomes of fitness, quality of life, depression, and nutrition status were evaluated.

RESULTS

The progressive resistance‐training intervention carried out during treatment did not significantly influence the primary outcome of body composition, despite a significant increase in weekly physical activity reported by the intervention group. A small‐to‐medium intervention effect was noted for some secondary outcomes, including fitness, quality of life, and nutrition status. Regardless of whether patients received the immediate or delayed progressive resistance‐training intervention, the analysis revealed a main effect of time on body composition, fitness, quality of life, depression, and nutritional scores.

CONCLUSIONS

Although the intervention during treatment did not reduce the loss of lean body mass, delaying the exercise program until after treatment completion was associated with improved intervention adherence, a finding with important clinical implications. Cancer 2016;122:1185–200. © 2016 American Cancer Society.
Bevacizumab beyond disease progression after first‐line treatment with bevacizumab plus chemotherapy in advanced nonsquamous non–small cell lung cancer (West Japan Oncology Group 5910L): An open‐label, randomized, phase 2 trial
Authors: Takeda Masayuki , Yamanaka Takeharu , Seto Takashi , Hayashi Hidetoshi , Azuma Koichi , Okada Morihito , Sugawara Shunichi , Daga Haruko , Hirashima Tomonori , Yonesaka Kimio , Urata Yoshiko , Murakami Haruyasu , Saito Haruhiro , Kubo Akihito , Sawa Toshiyuki , Miyahara Eiji , Nogami Naoyuki , Nakagawa Kazuhiko , Nakanishi Yoichi , Okamoto Isamu
Published: February 2016

BACKGROUND

Bevacizumab combined with platinum‐based chemotherapy has been established as a standard treatment option in the first‐line setting for advanced nonsquamous non–small cell lung cancer (NSCLC). However, there has been no evidence to support the use of bevacizumab beyond disease progression in such patients.

METHODS

West Japan Oncology Group 5910L was designed as a multicenter, open‐label, randomized, phase 2 trial of docetaxel versus docetaxel plus bevacizumab every 3 weeks for patients with recurrent or metastatic nonsquamous NSCLC whose disease had progressed after first‐line treatment with bevacizumab plus a platinum‐based doublet. The primary endpoint was progression‐free survival (PFS).

RESULTS

One hundred patients were randomly assigned to receive docetaxel (n = 50) or docetaxel plus bevacizumab (n = 50), and this yielded median PFS times of 3.4 and 4.4 months, respectively, with a hazard ratio (HR) of 0.71 and a stratified log‐rank P value of .058, which met the predefined criterion for statistical significance (P < .2). The median overall survival also tended to be longer in the docetaxel plus bevacizumab group (13.1 months; 95% confidence interval [CI], 10.6‐21.4 months) versus the docetaxel group (11.0 months; 95% CI, 7.6‐16.1 months) with an HR of 0.74 (95% CI, 0.46‐1.19; stratified log‐rank P = .11). No unexpected or severe adverse events were recorded.

CONCLUSIONS

Further evaluation of bevacizumab beyond disease progression is warranted for patients with advanced NSCLC whose disease has progressed after treatment with bevacizumab plus a platinum‐based doublet. Cancer 2016;122:1050–1059. © 2016 American Cancer Society
Switchable Hydrophobic Valve for Controlled Microfluidic Processing
Authors: Biswas Gokul Chandra , Watanabe Takahiro , Carlen Edwin T. , Yokokawa Masatoshi , Suzuki Hiroaki
Published: January 2016

A simple microfluidic valve, without any moving parts, is presented that can control solution flow on demand in microchannels of many different materials using a low‐power electric signal. Many independently operating valves can easily be integrated into complex microfluidic systems. The valve consists of a self‐assembled monolayer (SAM) formed on a platinum electrode that is incorporated directly in the microchannel. The normally‐on valve stops the solution flow due to a hydrophobic SAM on the electrode surface. The solution is allowed to pass the valve by applying a potential to the electrode, which removes the SAM due to reductive desorption. The valve operation is highly stable and has switching times of the order of 1 s. The valve is ideal for controlled solution manipulation in integrated micro‐analytical systems and autonomous microfluidic systems.
Metallomesogens with Luminescent Behaviour: Palladium Complexes Derived from Alkylamide Tetraarylporphyrins
Authors: Moura Nuno M. M. , Cuerva Cristián , Cavaleiro José A. S. , Mendes Ricardo F. , Almeida Paz Filipe A. , Cano Mercedes , Neves M. Graça P. M. S. , Lodeiro Carlos
Published: January 2016

A series of meso‐tetraaryl‐substituted free‐base porphyrins containing different numbers of alkyl amide chains with different lengths, as well as the corresponding palladium(II) and platinum(II) complexes, were prepared in good yields and were fully characterised. The crystal structure of the palladium(II) complex containing eight alkyl chains with five carbon atoms was unequivocally elucidated by means of single‐crystal XRD studies. The thermal behaviour of the new compounds was studied by polarised light optical microscopy and differential scanning calorimetry. Porphyrins with eight terminal alkyl chains containing five and eight carbon atoms, and the corresponding palladium(II) complexes, behave as liquid‐crystalline materials, exhibiting lamellar columnar mesophases at temperatures above 80 °C. The number of terminal alkyl chains and the palladium(II) metal centre play a key role in achieving mesomorphic behaviour.
Generalized OSTBC‐based subcarrier intensity‐modulated MIMO optical wireless communication system
Authors: Sharma Nikhil , Bansal Ankur , Garg Parul
Published: February 2016

In this paper, we analyze an optical wireless communication (OWC) system having a source and a destination node, equipped with multiple transmit and receive apertures, respectively. We utilize generalized orthogonal space‐time block codes (OSTBCs) of any arbitrary order and subcarrier intensity modulation scheme for data transmission over gamma–gamma (GG) fading optical links using M‐ary phase‐shift keying (PSK) constellation. A symbol‐wise decoding is utilized, and the closed‐form expression of the approximate average symbol error rate (SER) of multi‐aperture‐based OWC system is obtained for the generalized OSTBC and an arbitrary M‐PSK constellation. Using the derived SER expression, we analytically evaluate the diversity order and the coding gain of the OWC system with GG atmospheric turbulence. It has been shown by the numerical results that the maximum possible diversity is achieved by using the symbol‐wise maximum likelihood decoding in the destination. Copyright © 2016 John Wiley & Sons, Ltd.
s‐Block Metal Complexes with Bis‐ and Tris(pyrazolyl)methane and ‐methanide Ligands
Authors: Krieck Sven , Koch Alexander , Hinze Kay , Müller Christoph , Lange Juliane , Görls Helmar , Westerhausen Matthias
Published: January 2016

Substituted bis‐ and tris(pyrazolyl)methanes and ‐methanides are isoelectronic with the corresponding pyrazolyl‐substituted boranates, but the use of these Lewis bases in the coordination chemistry of the s‐block metals has attracted attention only quite recently. Many lithium and magnesium complexes have been isolated and characterized, but for the heavier alkali and alkaline earth metals much less information is available. Beryllium complexes are unknown, due to the toxicity of this lightest alkaline earth metal. The bis‐ and tris(pyrazolyl)methanes and ‐methanides act as multidentate ligands to the metal ions and commonly bind through the pyrazolyl bases. The presence of the very rare κ2N,κC coordination mode of the tris(pyrazolyl)methanides destabilizes these ligands and leads to their degradation. This microreview presents syntheses, molecular structures, and characteristic spectroscopic properties of s‐block metal complexes with bis‐ and tris(pyrazolyl)methane and ‐methanide ligands as well as with heteroscorpionate ligands. Furthermore, degradation of tris(pyrazolyl)methanides at heavy alkaline earth metals (especially of calcium) is discussed on the basis of experimental results and quantum chemical calculations.
Understanding Uncertainties in the Economic Feasibility of Transportation Fuel Production using Biomass Gasification and Mixed Alcohol Synthesis
Authors: Ou Longwen , Li Boyan , Dang Qi , Jones Susanne , Brown Robert , Wright Mark M.
Published: January 2016

This study evaluates uncertainties in the techno‐economic analysis of transportation fuel production from biomass gasification and mixed alcohol synthesis. Two scenarios are considered: a state‐of‐technology scenario and a target scenario with projected technological advances. Uncertainties of more than 10 parameters are investigated. The probability distributions of these parameters are estimated based on historical price data and experimental data. Data samples generated from the corresponding distribution are then utilized to run a Monte Carlo simulation. The results yield minimum fuel‐selling prices of $ 1.85 L−1 with a standard deviation of 0.13 for the state‐of‐technology scenario and $ 1.14 L−1 with a standard deviation of 0.11 for the target scenario, respectively. The feedstock price and internal rate of return (IRR) have significant impacts on the minimum fuel‐selling price in both scenarios. These findings are indicative of the reduction in biofuel cost and uncertainty achievable with increasing technology maturity.
Method for Increasing the Humidity in Polymer Electrolyte Membrane Fuel Cell
Authors: Carello M. , Vita A. De , Ferraris A.
Published: February 2016

The water content within the polymer electrolyte membrane is essential to have good proton conduction and high efficiency of a fuel cell system. In this paper a new technique to increase the fuel cell efficiency acting on the internal humidity will be presented. In order to understand the potentialities and the limitations of such technique, the method was studied in a theoretical approach and then applied on a proton exchange membrane fuel cell (1 kW PEMFC) that supplies the energy for the traction of a prototype vehicle, which took part in the last Shell Eco‐marathon competition. Finally has been verified that the membrane water content is related to the hydrogen consumption and for some applications (e.g., military single‐use equipment), the “filling” method could be advantageous over humidified system and non‐humidified systems. To ensure the proper success of the procedure it is also applied the differential method to fault detection.
Self‐other resonance, its control and prosocial inclinations: Brain–behavior relationships
Authors: Christov‐Moore Leonardo , Iacoboni Marco
Published: February 2016

Humans seem to place a positive reward value on prosocial behavior. Evidence suggests that this prosocial inclination is driven by our reflexive tendency to share in the observed sensations, emotions and behavior of others, or “self‐other resonance”. In this study, we examine how neural correlates of self‐other resonance relate to prosocial decision‐making. Subjects performed two tasks while undergoing fMRI: observation of a human hand pierced by a needle, and observation and imitation of emotional facial expressions. Outside the scanner, subjects played the Dictator Game with players of low or high income (represented by neutral‐expression headshots). Subjects’ offers in the Dictator Game were correlated with activity in neural systems associated with self‐other resonance and anticorrelated with activity in systems implicated in the control of pain, affect, and imitation. Functional connectivity between areas involved in self‐other resonance and top‐down control was negatively correlated with subjects’ offers. This study suggests that the interaction between self‐other resonance and top‐down control processes are an important component of prosocial inclinations towards others, even when biological stimuli associated with self‐other resonance are limited. These findings support a view of prosocial decision‐making grounded in embodied cognition. Hum Brain Mapp 37:1544‐1558, 2016. © 2016 Wiley Periodicals, Inc.