bluuebunny/crossref_metadata_2025 huggingface dataset:
Initiation of plate tectonics from post‐magma ocean thermochemical convection
Authors: Foley Bradford J. , Bercovici David , Elkins‐Tanton Linda T.
Published: October 2014

Leading theories for the presence of plate tectonics on Earth typically appeal to the role of present day conditions in promoting rheological weakening of the lithosphere. However, it is unknown whether the conditions of the early Earth were favorable for plate tectonics, or any form of subduction, and thus, how subduction begins is unclear. Using physical models based on grain‐damage, a grainsize‐feedback mechanism capable of producing plate‐like mantle convection, we demonstrate that subduction was possible on the Hadean Earth (hereafter referred to as proto‐subduction or proto‐plate tectonics), that proto‐subduction differed from modern day plate tectonics, and that it could initiate rapidly. Scaling laws for convection with grain‐damage show that though either higher mantle temperatures or higher surface temperatures lead to slower plates, proto‐subduction, with plate speeds of ≈1.75 cm/yr, can still be maintained in the Hadean, even with a CO2 rich primordial atmosphere. Furthermore, when the mantle potential temperature is high (e.g., above ≈2000 K), the mode of subduction switches to a “sluggish subduction” style, where downwellings are drip like and plate boundaries are diffuse. Finally, numerical models of post‐magma ocean mantle convection demonstrate that proto‐plate tectonics likely initiates within ∼100 Myr of magma ocean solidification, consistent with evidence from Hadean zircons. After the initiation of proto‐subduction, non‐plate‐tectonic “sluggish subduction” prevails, giving way to modern style plate tectonics as both the mantle interior and climate cool. Hadean proto‐subduction may hasten the onset of modern plate tectonics by drawing excess CO2 out of the atmosphere and cooling the climate.
Characteristics of tropical cyclones in high‐resolution models in the present climate
Authors: Shaevitz Daniel A. , Camargo Suzana J. , Sobel Adam H. , Jonas Jeffrey A. , Kim Daehyun , Kumar Arun , LaRow Timothy E. , Lim Young‐Kwon , Murakami Hiroyuki , Reed Kevin A. , Roberts Malcolm J. , Scoccimarro Enrico , Vidale Pier Luigi , Wang Hui , Wehner Michael F. , Zhao Ming , Henderson Naomi
Published: October 2014

The global characteristics of tropical cyclones (TCs) simulated by several climate models are analyzed and compared with observations. The global climate models were forced by the same sea surface temperature (SST) fields in two types of experiments, using climatological SST and interannually varying SST. TC tracks and intensities are derived from each model's output fields by the group who ran that model, using their own preferred tracking scheme; the study considers the combination of model and tracking scheme as a single modeling system, and compares the properties derived from the different systems. Overall, the observed geographic distribution of global TC frequency was reasonably well reproduced. As expected, with the exception of one model, intensities of the simulated TC were lower than in observations, to a degree that varies considerably across models.
Exploratory analysis of extremely low tropical cyclone activity during the late‐season of 2010 and 1998 over the western North Pacific and the South China Sea
Authors: Zhao Haikun , Chu Pao‐Shin , Hsu Pang‐Chi , Murakami Hiroyuki
Published: October 2014

This study attempts to understand why the tropical cyclone (TC) frequency over the western North Pacific and the South China Sea was so low in 2010 and 1998 even though a strong La Niña signal occurred in both years. We found that the TC frequency during the late‐season (October to December), not in the peak season (July to September), makes 2010 a record low year; the next lowest year is 1998. Specifically, four TCs were observed over the South China Sea (SCS) in the late‐season of 1998, but no TCs occurred over the SCS in the same season during 2010. The genesis potential index is used to help diagnose changes in environmental conditions for TC genesis frequency. Results indicate that the decreased low‐level vorticity makes the largest contribution to the decreased TC formation over the SCS. The second largest contribution comes from the enhanced vertical wind shear, with relatively small contributions from the negative anomaly in potential intensity and reduction in midlevel relative humidity. These observational results are consistent with numerical simulations using a state of the art model from the Meteorological Research Institute (MRI‐AGCM 3.2 Model). Numerical experiments show that the unfavorable conditions for sharply decreased TC formation during the late‐season over the SCS in 2010 mainly results from the sea surface temperature anomaly over the western North Pacific basin. This effect is partly offset by the sea surface temperature anomaly in the South Indian Ocean and Northern Indian Ocean basins.
Engine Thermal Management
Authors: Filipi Zoran , Jung Dohoy , Hoffman Mark
Published: October 2014

Internal combustion (IC) engines experience in‐cylinder gas temperatures of up to 2500°C during combustion, promoting heat transfer from the hot gases to the metal surfaces of the combustion chamber. Heat needs to be removed at relatively high rates to maintain proper engine component temperatures, and prevent failures that result from excessive thermal stresses, fatigue cracking, engine knocking combustion, and lubricant layer degradation.

The engine cooling system accomplishes the necessary heat rejection by circulating air or liquid coolant around the combustion chamber, absorbing heat from the engine, and subsequently dissipating the heat to the ambient. Heat rejection to the lubricant plays an important role too. A thorough understanding of heat transfer modes and pathways is necessary for the design of an effective engine cooling system.

The topics covered in this chapter are modes of engine heat transfer, modeling and experimental analysis of the heat transfer from the gas in the cylinder to the wall, heat transfer from the outer wall to coolant, semiempirical heat transfer correlations for engine cycle simulations, heat transfer from the piston rings to the cylinder liner, exhaust port heat transfer, cooling system functional requirements, air cooling, liquid cooling, coolant flow patterns through the cylinder block/head, cooling system components, temperature control in the engine with liquid cooling, automatic transmission cooling, as well as cooling system operation, integration, packaging, and management of the underhood air flow. Waste heat recovery is discussed at the end of the chapter as a special topic.
Cranktrain Development
Authors: Gilbert Ian P.
Published: October 2014

The crankshaft is responsible for the conversion of the linear motion of the piston into rotation that can be usefully passed to the rest of the vehicle drivetrain. As such, it can be seen as the heart of the engine. Although simple in appearance, optimization of the design of the crankshaft is fundamental to achieve an engine design that is efficient and refined, compact with minimum weight, reliable, and with lowest cost. This chapter explains the function and design considerations of the individual features of the crankshaft. Manufacturing processes are described starting from material selection for the casting or forging, moving through machining and onto surface treatment for wear and fatigue resistance.
Automotive Applications for Titanium
Authors: Jackson Martin
Published: October 2014

Titanium alloys are currently used in high performance vehicles in exhaust systems, suspension springs, and some engine components such as engine valves and connecting rods. They are employed owing to their attractive mechanical properties, such as high strength and fatigue resistance at moderately high temperatures. As titanium has half the density of steel, and better dynamic properties than aluminum, it is attractive for weight saving when high performance is necessary, such as in NASCAR and Formula One cars. Today, titanium is not currently employed in high production vehicles, owing its high cost, inherent from titanium's high affinity for oxygen during processing. However, at the turn of the century, a couple of hundred sets of titanium springs of alloy TIMETAL
®
LCB were employed by Volkswagen in their Lupo FSI economy car, but this is the greatest extent to its use in high production vehicles. The eventual high cost of the master alloy to produce this titanium alloy became the familiar Achilles heel for the automotive industry. Today, only 1000 tons/year are employed in the industry. Until a step change in the economics of titanium is created, it will continue to be restricted to the high performance vehicles.
Automotive Glazing
Authors: Kirwan Kerry
Published: October 2014

This chapter examines the background to automotive glazing and discusses how glazing systems within cars have become more sophisticated over time to afford a number of engineering opportunities. It also investigates the research that has been carried out into alternatives to glass and why they may not have been as successful as they were lauded. Finally, it discusses some of the more common technical issues that need to be considered when designing and engineering glazing systems.
Particle Formation and Models
Authors: Kittelson David , Kraft Markus
Published: October 2014

This chapter reviews work on aerosols originating from internal combustion engines with an emphasis on soot formation during combustion as well as formation of semi‐volatile and ash particles during combustion and subsequent cooling and dilution processes. Mathematical models of particle formation in engines and remaining modeling challenges are also discussed. Aerosols are formed during combustion in the cylinder, in the exhaust system, and after the tailpipe. Specific mechanisms include the injection of fuel, formation and oxidation of particles during combustion, exhaust gas recirculation (EGR), and condensation of semi‐volatiles. The role of fuels is discussed with respect to their ignition behavior as a consequence of mixture preparation in the cylinder and with respect to their sooting propensity. Models for the formation, growth, and oxidation of soot particles are presented and the most popular mathematical approaches for simulating particle emissions are introduced. Solid and semi‐volatile nucleation mode particles are also discussed in some detail. Key drivers in the formation of these particles are sulfur in the fuel and lubricating oil and metals in the lubricating oil. Particle emissions of different types of gasoline engines with and without aftertreatment are also discussed and compared with diesel engine emissions. Some of the shortcomings of the current models and future research areas are highlighted at the end.
Urban Traffic Management
Authors: Fellendorf Martin
Published: October 2014

Traffic management contains all measures suited to guide and control any kind of trips of freight or persons independent of trip purpose and mode of transport. Traffic signal control is the most widely and most effective operational measure to control individual vehicle movements and guide traffic streams in dense urban networks. Signal control measures can become operational by quick adaptation of green periods. This chapter introduces the basic concept of traffic signal control and some new advances imposed by state‐of‐the‐art Urban Traffic Control Systems and the upcoming technology of cooperative systems. Other urban control methods such as contraflow systems and parking guidance systems are mentioned without much details.
Advanced Highway Management Systems
Authors: Listl Gerhard , Obenberger Jon
Published: October 2014

Advanced highway management systems (AHMS) belong to the established instruments of road transport telematics. They aim for improving the safety and mobility of travelers. Through the provision of of travel and roadway condition information and use of traffic control strategies at junctions and sections (supply management), their aim is to optimize the flow of traffic and use of the roadways cross section influencing the traffic demand in space and time (demand management) on the basis of current and projected traffic, roadway and weather conditions. The article deals first with the structure and objectives of advanced highway management systems. Following a brief introduction into traffic flow on highways, general approaches of demand and supply management followed by the range of operational strategies and the supporting AHMS functions are described. One focus is on the integrated and cross‐system‐related active traffic management approaches and the potential benefits of sharing basic safety messages and related information between connected vehicles and AHMS's. This requires agencies to establish and provide the resources to establish the strategic vision, policies, procedures, systems and strategies to implement and actively manage and operate roadways. Information is also provided for system planning and implementation, quality management, and recent developments and innovations in the field of AHMS.
Starter
Authors: Endo Suehiro , Tajima Susumu
Published: October 2014

This chapter describes the structure of the starter motor as a vehicle starting device and its feature. ISS (idle stop and start systems) and ISG (integrated starter generator) are explained as the newest engine starting systems.
Chassis
ECU
(Steering)
Authors: Mori Yutaka , Nishimoto Mitsuhiko
Published: October 2014

The ECU, described here, is electric power steering, which is intended to control the motor in response to the input such as sensor signal to assist the driver's steering effort. The steering system has been developed from the conventional manual steering, steered only by the driver's effort, in contrast to the hydraulic power steering utilizing the hydraulic power. However, recently, the electric power steering with excellent energy saving is becoming mainstream. Here, the type of the steering system and the function of the entire steering system are described, and also electrical units used in electric power steering, especially, the steering‐specific function in the ECU, are introduced. Steering feeling control and trends in safety, including fail‐safe systems, risk mitigation, and so on, are also introduced.
Various Kinds of Actuators and Signal Interfaces
Authors: Naito Shinichi
Published: October 2014

Advances in technology are increasing the variety and sophistication of a wide range of actuators used in vehicles. The main types of actuators are motors, solenoids, and relays that use electromagnetic force and piezoactuators that use the piezoelectric effect. This chapter describes these actuators and examples of their application, focusing on motors. It also briefly outlines signal interfaces, which play an important role in the use of all types of actuators.
Vehicle Vibration and Harshness
Authors: García‐Bonito Juan J. , Fernández Ismael
Published: October 2014

Vibrationrefers to a mechanical oscillation in relation to a reference position. It is not only a phenomenon of nuisance, but it can also cause machines or structures to break. The word comfort is used to describe the absence of discomfort and a good feeling of well‐being. In order to better understand the relation between vibration and comfort, systematic experimental studies of the extent to which variations of vibration stimuli produce changes in a subject's judgments of discomfort have to be carried out. There is no universally accepted methodology for evaluating the level of comfort. Consequently, each car manufacturer has developed its own method for testing and processing the experimental data in order to get information about the comfort of its vehicles.

In recent years, engineering techniques have made it possible to improve many areas of design and, as a consequence, vehicle comfort has improved. However, a lot of tests still have to be done to quantify the comfort of a vehicle or to compare the influence of different components or different configurations on comfort during the development phase. It is also very useful to compare different vehicles of the same market segment in order to establish their position in the market and to make the appropriate decisions.
Cyclic‐Disulfide‐Based Prodrugs for Cytosol‐Specific Drug Delivery
Authors: Butora Gabor , Qi Ning , Fu Wenlang , Nguyen Truyen , Huang Hsueh‐Cheng , Davies Ian W.
Published: October 2014

The cytosolic conversion of therapeutically relevant nucleosides into bioactive triphosphates is often hampered by the inefficiency of the first kinase‐mediated step. Nucleoside monophosphate prodrugs can be used to bypass this limitation. Herein we describe a novel cyclic‐disulfide class of nucleoside monophosphate prodrugs with a cytosol‐specific, reductive release trigger. The key event, a charge‐dissipating reduction‐triggered cyclodeesterification leads to robust cytosolic production of the cyclic 3′,5′‐monophosphate for downstream enzymatic processing. The antiviral competence of the platform was demonstrated with an O‐benzyl‐1,2‐dithiane‐4,5‐diol ester of 2′‐C‐methyluridine‐3′,5′‐phosphate. Both in vitro and in vivo comparison with the clinically efficacious ProTide prodrug of 2′‐deoxy‐2′‐α‐fluoro‐β‐C‐methyluridine is provided. The cytosolic specificity of the release allows for a wide range of potential applications, from tissue‐targeted drug delivery to intracellular imaging.
Enantioselektive schutzgruppenfreie Totalsynthese von Sarpagin‐ Alkaloiden – ein generalisierter Zugang
Authors: Krüger Sebastian , Gaich Tanja
Published: October 2014

Die Totalsynthese der drei Sarpagin‐Alkaloide (+)‐Vellosimin (1), (+)‐N‐Methylvellosimin (3) und (+)‐10‐Methoxyvellosimin (8) folgt einer gemeinsamen Route. Die Synthese umfasst 8 Stufen ausgehend von Verbindung 13, ist weitgehend schutzgruppenfrei und beinhaltet als Schlüsselschritte eine [5+2]‐Cycloaddition und eine Ringerweiterung, bevor im letzten Schritt der charakteristische Indol‐Heterocyclus aufgebaut wird. Da sich die einzelnen Naturstoffe im Substitutionsmuster am Indolsystem unterscheiden, konnten alle Mitglieder der Alkaloid‐Familie ausgehend von der gemeinsamen Vorstufe 10 über eine Fischer‐Indolsynthese mit verschieden substituierten Phenylhydrazinen (15–17) hergestellt werden. Die gemeinsame Route zu allen Sarpagin‐Alkaloiden hat den großen Vorteil, dass die einzelnen Syntheseoperationen nur einmal optimiert werden müssen und daher Substituenteneffekte in den einzelnen Reaktionen ausgeschlossen sind.
In Situ Vesicle Formation by Native Chemical Ligation
Authors: Brea Roberto J. , Cole Christian M. , Devaraj Neal K.
Published: October 2014

Phospholipid vesicles are of intense fundamental and practical interest, yet methods for their de novo generation from reactive precursors are limited. A non‐enzymatic and chemoselective method to spontaneously generate phospholipid membranes from water‐soluble starting materials would be a powerful tool for generating vesicles and studying lipid membranes. Here we describe the use of native chemical ligation (NCL) to rapidly prepare phospholipids spontaneously from thioesters. While NCL is one of the most popular tools for synthesizing proteins and nucleic acids, to our knowledge this is the first example of using NCL to generate phospholipids de novo. The lipids are capable of in situ synthesis and self‐assembly into vesicles that can grow to several microns in diameter. The selectivity of the NCL reaction makes in situ membrane formation compatible with biological materials such as proteins. This work expands the application of NCL to the formation of phospholipid membranes.
The τ Decomposition Method for PID Controllers of First Order Delayed Unstable Processes
Authors: Cai Tiao‐Yang , Zhang Hua‐Guang , Yang Fei‐Sheng , Xie Xiang‐Peng
Published: October 2014

The stabilization of first‐order delayed (FOD) unstable processes with proportional–integral–derivative (PID) controllers is considered, and all the feasible PID controllers are determined. Different from the existing results which are based on the D‐partition technique and partitioning complex's real and imaginary parts, a novel procedure enlightened by the τ decomposition method is proposed to characterize the space of controller parameters. Generally speaking, the parameter space is mainly divided into four regions: delay independent stable region, delay independent unstable region, delay interval dependent stable region, and delay interval dependent unstable region. The depiction of the space partition boundaries and the determination of stable intervals become the main problems. In our work, these boundaries are related to the existence of the purely imaginary roots (PIRs) of the systems' characteristic equation, and the determination of stable intervals refers to the number and value of the PIRs. Thus, the key points are the number and calculation of PIRs. According to our discussion, analytical results on both topics are obtained in explicit form. Finally, vivid numerical simulations are given to illustrate the results.
Transfecting pDNA to E. coli DH5α using bovine serum albumin nanoparticles as a delivery vehicle
Authors: Wagh Jitendra , Patel Kuldeep J. , Soni Parth , Desai Krutika , Upadhyay Pratik , Soni Hemant P.
Published: October 2014

We describe the formulation of bovine serum albumin nanoparticles (BSA‐NPs) by the coacervation method using surfactants. Plasmids (pUC18, pUC18egfp and pBBR1MCS‐2) isolated from E. coli were incorporated into the BSA matrix by incubating in albumin solution prior to formulation of NPs. Plasmid incorporation was calculated by % yield, entrapment efficiency, DNA loading capacity and release of entrapped DNA by comparing with blank NPs. BSA‐DNA binding studies were carried out by using fluorescence spectroscopy and Fourier Transform Infra Red Spectroscopy (FT‐IR). The surface charge distribution of the NPs loaded with plasmid was calculated using zeta potential. The photoluminescence of BSA‐NPs was quenched when loaded with pDNA, confirming the interaction of DNA with BSA. Altogether, these results provide evidences for the excellent DNA carrying efficiency of BSA‐NPs without loss of plasmid's integrity. The NPs were used to transfect E. coli DH5α strain lacking ampicillin resistance. They, however, showed ampicillin resistance subsequent to transfection with plasmid encoding ampicillin resistance gene. Effect of transfection was confirmed by confocal microscopy and by the isolation of the plasmid by agarose gel electrophoresis from the transfected bacterial culture. This study clearly demonstrates the efficacy of BSA‐NPs as delivery vehicle for pDNA transfection. Copyright © 2014 John Wiley & Sons, Ltd.
Slippage of a Porphyrin Macrocycle over Threads of Varying Bulkiness: Implications for the Mechanism of Threading Polymers through a Macrocyclic Ring
Authors: Deutman Alexander B. C. , Varghese Shaji , Moalin Mohamed , Elemans Johannes A. A. W. , Rowan Alan E. , Nolte Roeland J. M.
Published: October 2014

Threading of a polymer through a macrocyclic ring may occur directly, that is, by finding the end of the polymer chain, or by a process in which the polymer chain first folds and then threads through the macrocyclic ring in a hairpin‐like conformation. We present kinetic and thermodynamic studies on the threading of a macrocyclic porphyrin receptor (H21) onto molecular threads that are blocked on one side and are open on the other side. The open side is modified by groups that vary in ease of folding and in bulkiness. Additionally, the threads contain a viologen binding site for the macrocyclic receptor, which is located close to the blocking group. The rates of threading of H21 were measured under various conditions, by recording as a function of time the quenching of the fluorescence of the porphyrin, which occurs when receptor H21 reaches the viologen binding site. The kinetic data suggest that threading is impossible if the receptor encounters an open side that is sterically encumbered in a similar way as a folded polymer chain. This indicates that threading of polymers through macrocyclic compounds through a folded chain mechanism is unlikely.
A Closer Look at Spontaneous Mirror Symmetry Breaking in Aldol Reactions
Authors: Valero Guillem , Ribó Josep M. , Moyano Albert
Published: October 2014

The aldol reaction between acetone and 4‐nitrobenzaldehyde run in the nominal absence of any enantioselective catalyst was monitored by chiral HPLC with the aid of an internal standard. The collected data show the presence of a detectable initial enantiomeric excess of the aldol product in the early stages of the reaction in about 50 % of the experiments. Only a small fraction of the reaction contained the non‐racemic aldol product after 24 h. This temporary emergence of natural optical activity could be the signature of a coupled reaction network that leads to a spontaneous mirror‐symmetry‐breaking process, which originates at very low conversions (i.e., strongly depends on events taking place at the very first stages of the process). The reaction is not autocatalytic in the aldol product, which rules out a simple Frank‐type reaction network as the source of the observed symmetry breaking. On the other hand, the isolation and characterisation of a double‐aldol adduct suggested a reaction network that involved both indirect autocatalysis and indirect mutual inhibition between the enantiomers of the reaction product.
Preparation of Thermocleavable Conjugates Based on Ansamitocin and Superparamagnetic Nanostructured Particles by a Chemobiosynthetic Approach
Authors: Mancuso Lena , Knobloch Tobias , Buchholz Jessica , Hartwig Jan , Möller Lena , Seidel Katja , Collisi Wera , Sasse Florenz , Kirschning Andreas
Published: October 2014

A combination of mutasynthesis, precursor‐directed biosynthesis and semisynthesis provides access to new ansamitocin derivatives including new nanostructured particle–drug conjugates. These conjugates are based on the toxin ansamitocin and superparamagnetic iron oxide–silica core shell particles. New ansamitocin derivatives that are functionalized either with alkynyl‐ or azido groups in the ester side chain at C‐3 are attached to nanostructured iron oxide core–silica shell particles. Upon exposure to an oscillating electromagnetic field these conjugates heat up and the ansamitocin derivatives are released by a retro‐Diels–Alder reaction. For example, one ansamitocin derivative exerts strong antiproliferative activity against various cancer cell lines in the lower nanomolar range while the corresponding nanostructured particle‐drug conjugate is not toxic. Therefore, these new conjugates can serve as dormant toxins that can be employed simultaneously in hyperthermia and chemotherapy when external inductive heating is applied.
One‐Pot Synthesis of 2,5‐Dihydropyrroles from Terminal Alkynes, Azides, and Propargylic Alcohols by Relay Actions of Copper, Rhodium, and Gold
Authors: Miura Tomoya , Tanaka Takamasa , Matsumoto Kohei , Murakami Masahiro
Published: October 2014

Relay actions of copper, rhodium, and gold formulate a one‐pot multistep pathway, which directly gives 2,5‐dihydropyrroles starting from terminal alkynes, sulfonyl azides, and propargylic alcohols. Initially, copper‐catalyzed 1,3‐dipolar cycloaddition of terminal alkynes with sulfonyl azides affords 1‐sulfonyl‐1,2,3‐triazoles, which then react with propargylic alcohols under the catalysis of rhodium. The resulting alkenyl propargyl ethers subsequently undergo the thermal Claisen rearrangement to give α‐allenyl‐α‐amino ketones. Finally, a gold catalyst prompts 5‐endo cyclization to produce 2,5‐dihydropyrroles.
Phosphinothiolates as Ligands for Polyhydrido Copper Nanoclusters
Authors: Huertos Miguel A. , Cano Israel , Bandeira Nuno A. G. , Benet‐Buchholz Jordi , Bo Carles , van Leeuwen Piet W. N. M.
Published: October 2014

Invited for the cover of this issue is the group of Piet W. N. M. van Leeuwen at the Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain. The cover was designed by Miguel and the sun represents the photoactivity of the complex, resulting in the production of hydrogen. Read the full text of the article at 10.1002/chem.201404763.
Redox Switching in Ethenyl‐Bridged Bisphospholes
Authors: Arkhypchuk Anna I. , Mijangos Edgar , Lomoth Reiner , Ott Sascha
Published: October 2014

A 2e−/2H+ redox platform has been implemented in the ethenyl‐bridged bisphosphol‐3‐ol 1 to afford the first phospholes that feature chemically reversible oxidations. Oxidation of the title compounds to the corresponding bisphosphol‐3‐one 2 leads to a change in conjugation topology and a concomitant hypsochromic shift of the lowest‐energy absorption maximum by 100 nm. Electrochemical oxidation proceeds without any detectable intermediates, whereas the deprotonated form of 1 can be observed in an aprotic medium during the reduction of 2. This dianionic intermediate 3 is characterized by end absorptions that are bathochromically shifted by circa 200 nm compared to those of 2.
“Nanorust”‐catalyzed Benign Oxidation of Amines for Selective Synthesis of Nitriles
Authors: Jagadeesh Rajenahally V. , Junge Henrik , Beller Matthias
Published: October 2014

Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable “nanorust” (nanoscale Fe2O3)‐based catalysts applying molecular oxygen.
A Gemini Quaternary Ammonium Poly (ether ether ketone) Anion‐Exchange Membrane for Alkaline Fuel Cell: Design, Synthesis, and Properties
Authors: Si Jiangju , Lu Shanfu , Xu Xin , Peng Sikan , Xiu Ruijie , Xiang Yan
Published: October 2014

To reconcile the tradeoff between conductivity and dimensional stability in AEMs, a novel Gemini quaternary ammonium poly (ether ether ketone) (GQ‐PEEK) membrane was designed and successfully synthesized by a green three‐step procedure that included polycondensation, bromination, and quaternization. Gemini quaternary ammonium cation groups attached to the anti‐swelling PEEK backbone improved the ionic conductivity of the membranes while undergoing only moderate swelling. The grafting degree (GD) of the GQ‐PEEK significantly affected the properties of the membranes, including their ion‐exchange capacity, water uptake, swelling, and ionic conductivity. Our GQ‐PEEK membranes exhibited less swelling (≤40 % at 25–70 °C, GD 67 %) and greater ionic conductivity (44.8 mS cm−1 at 75 °C, GD 67 %) compared with single quaternary ammonium poly (ether ether ketone). Enhanced fuel cell performance was achieved when the GQ‐PEEK membranes were incorporated into H2/O2 single cells.
Tick‐borne encephalitis virus subtypes emerged through rapid vector switches rather than gradual evolution
Authors: Kovalev Sergey Y. , Mukhacheva Tatyana A.
Published: October 2014

Tick‐borne encephalitis is the most important human arthropod‐borne virus disease in Europe and Russia, with an annual incidence of about 13 thousand people. Tick‐borne encephalitis virus (TBEV) is distributed in the natural foci of forest and taiga zones of Eurasia, from the Pacific to the Atlantic coast. Currently, there are three mutually exclusive hypotheses about the origin and distribution ofTBEVsubtypes, although they are based on the same assumption of gradual evolution. Recently, we have described the structure ofTBEVpopulations in terms of a clusteron approach, a clusteron being a structural unit of viral population [Kovalev and Mukhacheva (2013)Infect. Genet. Evol., 14, 22–28]. This approach allowed us to investigate questions ofTBEVevolution in a new way and to propose a hypothesis of quantum evolution due to a vector switch. We also consider a possible mechanism for this switch occurring in interspecific hybrids of ticks. It is necessarily accompanied by a rapid accumulation of mutations in the virus genome, which is contrary to the generally accepted view of gradual evolution in assessing the ages ofTBEVpopulations. The proposed hypothesis could explain and predict not only the formation of new subtypes, but also the emergence of new vector‐borne viruses.
Reduced executive and default network functional connectivity in cigarette smokers
Authors: Weiland Barbara J. , Sabbineni Amithrupa , Calhoun Vince D. , Welsh Robert C. , Hutchison Kent E.
Published: October 2014

Altered functional connectivity has been associated with acute and chronic nicotine use. Connectivity alterations, specifically in the right and left executive control networks (RECN/LECN) and the default mode network (DMN), may contribute to the addiction cycle. The objective of this study was to determine if executive control network (ECN) and DMN connectivity is different between non‐smokers and smokers and whether reductions in connectivity are related to chronic cigarette use. The RECN, LECN, and DMN were identified in resting state functional magnetic resonance imaging data in 650 subjects. Analyses tested for group differences in network connectivity strength, controlling for age and alcohol use. There was a significant group effect on LECN and DMN connectivity strength with smokers (n = 452) having lower network strengths than non‐smokers (n = 198). Smokers had lower connectivity than non‐smokers associated with key network hubs: the dorsolateral prefrontal cortex, and parietal nodes within ECNs. Further, ECN connectivity strength was negatively associated with pack years of cigarette use. Our data suggest that chronic nicotine use negatively impacts functional connectivity within control networks that may contribute to the difficulty smokers have in quitting. Hum Brain Mapp 36:872–882, 2015. © 2014 Wiley Periodicals, Inc.
Stimulus dependence of contralateral dominance in human auditory cortex
Authors: Gutschalk Alexander , Steinmann Iris
Published: October 2014

The auditory system is often considered to show little contralateral dominance but physiological reports on the contralateral dominance of activity evoked by monaural sound vary widely. Here, we show that part of this variation is stimulus‐dependent: blood oxygen level dependent (BOLD) responses to 32 s of monaurally presented unmodulated noise (UN) showed activation in contralateral auditory cortex (AC) and deactivation in ipsilateral AC compared to nonstimulus baseline. Slow amplitude‐modulated (AM) noise evoked strong contralateral activation and minimal ipsilateral activation. The contrast of AM–versus‐UN was used to separate fMRI activity related to the slow amplitude modulation per se. This difference activation was bilateral although still stronger in contralateral AC. In magnetoencephalography (MEG), the response was dominated by the steady‐state activity phase locked to the amplitude modulation. This MEG activity showed no consistent contralateral dominance across listeners. Subcortical BOLD activation was strongly contralateral subsequent to the superior olivary complex (SOC) and showed no significant difference between modulated and UN. An acallosal participant showed similar fMRI activation as the group, ruling transcallosal transmission an unlikely source of ipsilateral enhancement or ipsilateral deactivation. These results suggest that ascending activity subsequent to the SOC is strongly dominant contralateral to the stimulus ear. In contrast, the part of BOLD and MEG activity related to slow amplitude modulation is more bilateral and only observed in AC. Ipsilateral deactivation can potentially bias measures of contralateral BOLD dominance and should be considered in future studies. Hum Brain Mapp 36:883–896, 2015. © 2014 Wiley Periodicals, Inc.
Osteocalcin/fibronectin‐functionalized collagen matrices for bone tissue engineering
Authors: Kim S. G. , Lee D. S. , Lee S. , Jang J.‐H.
Published: October 2014

Collagen is the most abundant protein found in the extracellular matrix and is widely used to build scaffolds for biomedical applications which are the result of its biocompatibility and biodegradability. In the present study, we constructed a rhOCN/FNIII9‐10 fusion protein and rhOCN/FNIII9‐10‐functionalized collagen matrices and investigated the potential value for bone tissue engineering. In vitro studies carried out with preosteoblastic MC3T3‐E1 cells showed that rhOCN/FNIII9‐10 fusion protein promoted cell adhesion and the mRNA levels of osteogenic markers including osteocalcin, runt‐related transcription factor 2, alkaline phosphatase (ALP), and collagen type I. In addition, rhOCN/FNIII9‐10‐functionalized collagen matrices showed significant induction of the ALP activity more than rhFNIII9‐10‐functionalized collagen matrices or collagen matrices alone. These results suggested that rhOCN/FNIII9‐10‐functionalized collagen matrices have potential for bone tissue engineering. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 103A: 2133–2140, 2015.
Study of Adsorption of Janus Green B and Methylene Blue on Nanocrystalline Cellulose
Authors: Samiey Babak , Tehrani Abbas Dadkhah
Published: October 2014

Received: Feb. 20, 2014

Accepted: Jun. 3, 2014
Thermodynamic Insight into Protein Aggregation Using a Kinetic Ising Model
Authors: Tsai Min‐Yeh , Yuan Jian‐Min , Lin Sheng‐Hsien
Published: October 2014

In this work, we present a kinetic analysis for protein aggregation using the kinetic Ising model, which serves as a new application of a previously proposed model [Liang et al., J. Chin. Chem. Soc.­ 2003, 50, 335]. Considering protein as a single spin unit, we map two states of a unit to the aggregation‐prone (AP) and the fibril (F) states. This work shows that the model can successfully capture the nucleation‐growth features of protein aggregation from experiments, which offers thermodynamic interpretations of aggregation properties, such as lag‐time and fibril stability.
Investigation of Luminescence Properties of Eu3+, Dy3+ and Gd3+ Doped MgAl2Si2O8 Red‐emitting Phosphors
Authors: Öztürk Esra , Kalaycioglu Nilgun Ozpozan , Uzun Erdem
Published: October 2014

Rare‐earth‐doped aluminosilicates of alkaline earth MgAl2Si2O8: Eu3+, Dy3+ and MgAl2Si2O8: Eu3+, Gd3+ were synthesized by the solid state reaction method at 1300 oC. The phosphors were characterized by X‐ray powder diffraction (XRD), photoluminescence (PL), thermoluminescence (TL) and scanning electron microscopy (SEM). X‐ray powder diffraction studies show that the phosphors were crystallized in the triclinic crystal system. The phosphors show characteristic broad band phosphorescence of Eu3+. This broad band phosphorescence has red emission bands in the range of 580–705 nm corresponding to 5D0 → 7Fj (j:0,2,3,4) transitions of Eu3+.
Therapeutic efficacy of splenectomy is attenuated by necroinflammation of the liver in patients with liver cirrhosis
Authors: Kondo Reiichiro , Kage Masayoshi , Ogata Toshiro , Nakashima Osamu , Akiba Jun , Nomura Yoriko , Yano Hirohisa
Published: October 2014

Background

Splenectomy is a therapy for thrombocytopenia caused by hypersplenism with liver cirrhosis. However, the determinant of therapeutic outcomes for this complication has not yet been fully clarified.

Methods

We studied the laboratory findings of 55 patients who underwent splenectomy for hypersplenism with liver cirrhosis. In addition, we examined the histopathological findings of hepatosplenic tissues of nine patients who underwent hepatectomy for hepatocellular carcinoma and splenectomy for hypersplenism with liver cirrhosis on one stage surgery. The locations of platelets in hepatosplenic tissues were identified by immunohistochemistry. We used monoclonal antibody against CD41.

Results

Among 55 patients, 40 patients had high serum alanine aminotransferase (ALT) level (≧38 IU/l). Blood platelet count after splenectomy of patients with high serum ALT level were significantly lower than those of patients with low serum ALT level (P = 0.02). Histopathologically, platelet area of the liver tissues was positively correlated with hepatic inflammation (P = 0.02). Platelet area of the liver tissues was negatively correlated with blood platelet count after splenectomy (P = 0.03).

Conclusions

Hepatic inflammation contributes to the accumulation of platelets in liver; therefore, in patients with high serum ALT level, improvement of thrombocytopenia by the elimination of hypersplenism was limited.
Endoscopic management of walled‐off pancreatic necrosis
Authors: Voermans Rogier P. , Besselink Marc G. , Fockens Paul
Published: October 2014

Endoscopic management of infected walled‐off pancreatic necrosis is increasingly being performed. Although the role of the interventional endoscopist in treating necrotizing pancreatitis is growing, a multidisciplinary team including dedicated surgeons and interventional radiologists is a condition sine qua non for optimal patient management. Optimal management starts with a correct diagnosis with accurate description of the extent and nature of the inflammatory changes according to the recently updated criteria. This is important to consequently select the correct patients for the correct intervention at the correct interval after onset. When a decision is made to endoscopically intervene in a patient with (infected) pancreatic necrosis, the actual endoscopic technique does not differ much from the first retrospective series published a decade ago. Although endoscopic intervention for pancreatic necrosis is increasingly performed, evidence for superiority of endoscopic treatment over other techniques is still lacking. Dedicated endoscopic accessories for optimal drainage and necrosectomy are still lacking as well. This review provides an overview of current status, technique and recent innovations of endoscopic treatment of walled‐off pancreatic necrosis.
Comparative analysis of sialendoscopy, sonography, and CBCT in the detection of sialolithiasis
Authors: Schwarz David , Kabbasch Christoph , Scheer Martin , Mikolajczak Stefanie , Beutner Dirk , Luers Jan C.
Published: October 2014

Objectives/Hypothesis

The diagnosis of sialolithiasis is, along with clinical presentation, based on different imaging techniques and more invasive procedures such as sialendoscopy. The aim of the study was to analyze the potential of cone beam computed tomography (CBCT) for the diagnosis of sialolithiasis and to compare the results with those of sonography and sialendoscopy.

Study Design

Retrospective analysis.

Methods

The data of 43 patients with suspected sialolithiasis were evaluated retrospectively. All patients had CBCT and sonographic imaging and received sialendoscopy to confirm and possibly treat sialolithiasis.

Results

Sonography, CBCT, and sialendoscopy together indicated sialolithiasis in 33 patients. The mean maximum diameter of the extracted sialoliths did not significantly differ between the three diagnostics. Each diagnostic tool showed an excellent specificity and positive predictive value. Sensitivity and negative predictive value were best in sialendoscopy (94% resp. 83%), followed by CBCT (79% resp. 56%) and then sonography (70% resp. 47%).

Conclusion

The results revealed that CBCT is capable of diagnosing sialoliths in general and tended to be more sensitive than sonography. However, in view of the radiation exposure, the use of CBCT must be critically weighed and should not be used as a primary option.

Level of Evidence

4. Laryngoscope, 125:1098–1101, 2015
HOPX is methylated and exerts tumour‐suppressive function through Ras‐induced senescence in human lung cancer
Authors: Chen Yuan , Yang Linlin , Cui Tiantian , Pacyna‐Gengelbach Manuela , Petersen Iver
Published: October 2014

HOPX acts as a tumour suppressor in various cancers. However, the regulation of HOPX in human lung cancer as well as the mechanism underlying its tumour‐suppressive function has not yet been well elucidated. Here we investigated the epigenetic regulation and molecular mechanism by which HOPX exerts growth inhibitory effects. We found that HOPX was down‐regulated in 12 out of 13 lung cancer cell lines and in 69 out of 120 primary lung tumours at mRNA and protein levels. Patients with lung adenocarcinoma (ADC) exhibited significantly more positive staining of HOPX protein compared with lung squamous cell carcinoma (SCC) (p =0.036). Again in ADC, patients with higher HOPX expression had a significantly longer disease‐free survival (p =0.001). Methylation analysis showed that down‐regulation of HOPX was associated with DNA methylation (p =0.011). To analyse the function of HOPX in lung cancer cells, stable transfection with an expression vector of HOPX was performed. It turned out that HOPX inhibited tumour cell proliferation rate, migration, and invasion, and, more interestingly, forced expression of HOPX enhanced cellular senescence via activation of oncogenic Ras and the downstream MAPK pathway, which in turn led to decreased MDM2 and increased p21. On the contrary, knockdown of HOPX by siRNA resulted in reduced Ras activity, inactivation of the MAPK pathway, and decreased p21 levels, accompanied by reduced cellular senescence. Additionally, the HOPX‐induced senescence pathway was also active in human bronchial epithelial cells. Taken together, our data suggest that down‐regulation of HOPX was related to DNA methylation and that HOPX exerts tumour‐suppressive activity by oncogenic Ras‐induced cellular senescence in lung cancer cells. Copyright © 2014 Pathological Society of Great Britain and Ireland. Published by John Wiley & Sons, Ltd.
Fibrodysplasia ossificans progressiva: bilateral hallux valgus on ultrasound a clue for the first prenatal diagnosis for this condition—clinical report and review of the literature
Authors: Maftei Catalina , Rypens Françoise , Thiffault Isabelle , Dubé Johanne , Laberge Anne‐Marie , Lemyre Emmanuelle
Published: October 2014

What's already known about this topic?

Fibrodysplasia ossificans progressiva (FOP) (MIM: 135100) is a very rare autosomal dominant condition with a prevalence of 1:2,000,000.

The clinical picture is characterized by congenital malformations of the great toes and progressive disabling heterotopic ossification.

The genetic explanation is an activating mutation in the ACVR1, a bone morphogenetic protein type I receptor, which promotes osteogenic differentiation of connective tissue progenitor cells.

What does this study add?

We present the first case of prenatal diagnosis of FOP on ultrasound findings.

Fetal bilateral hallux valgus, seen on second‐trimester ultrasound prompted the clinicians to consider this diagnosis even though family history was negative for FOP. The fetus had the recurrent c.617G > A mutation in ACVR1 gene.

This case illustrates that FOP should be considered in the differential diagnosis of fetal hallux valgus to provide appropriate genetic counseling.