bluuebunny/crossref_metadata_2025 huggingface dataset:
Policy regimes and funding schemes to support investment for next‐generation biofuels in the USA and the EU‐27
Authors: Panoutsou Calliope , Bauen Ausilio , Duffield Jim
Published: August 2013

The production of next‐generation biofuels both in the EU‐27 and the USA involves producing biofuels beyond the conventional sugar, starch, vegetable oils, and animal‐fat‐based biofuels now produced commercially. Next‐generation biofuels can be derived from non‐food crops or agricultural residues, fast‐growing trees, forestry, and municipal wastes, etc., and include (cellulosic) ethanol, butanol, methanol, dimethyl ether (DME), Fischer‐Tropsch diesel, upgraded pyrolysis oils, microbial drop‐in gasoline and diesel substitutes, and biofuels made from microbial oils and algae.

The context of policy development for next‐generation biofuels both in the USA and the EU‐27 is based on the evidence that as demand for biofuels is growing and both the market and policies become more ambitious, a broader variety of feedstocks are needed to meet increasing production and use goals. At the moment, in both regions, policies to support conventional biofuels are still in place, but new strategies are being adopted at a fast rate to build a bridge from first‐generation to next‐generation biofuels and ensure sustainable supply.

This paper presents the background and rationale for the current policy regimes and funding schemes in the USA and EU‐27 in relation to next‐generation biofuels, gives an update of the current market developments and provides a set of recommendations on the key issues that future policy formation should take into account to efficiently translate the ‘ambitious’ targets into a commercialization prospects. © 2013 Society of Chemical Industry and John Wiley & Sons, Ltd
Challenges in the estimation of greenhouse gas emissions from biofuel‐induced global land‐use change
Authors: Warner Ethan , Zhang Yimin , Inman Daniel , Heath Garvin
Published: August 2013

The estimation of greenhouse gas (GHG) emissions from a change in land‐use and management resulting from growing biofuel feedstocks has undergone extensive – and often contentious – scientific and policy debate. Emergent renewable fuel policies require life cycle GHG emission accounting that includes biofuel‐induced global land‐use change (LUC) GHG emissions. However, the science of LUC generally, and biofuels‐induced LUC specifically, is nascent and underpinned with great uncertainty. We critically review modeling approaches employed to estimate biofuel‐induced LUC and identify major challenges, important research gaps, and limitations of LUC studies for transportation fuels. We found LUC modeling philosophies and model structures and features (e.g. dynamic vs. static model) significantly differ among studies. Variations in estimated GHG emissions from biofuel‐induced LUC are also driven by differences in scenarios assessed, varying assumptions, inconsistent definitions (e.g. LUC), subjective selection of reference scenarios against which (marginal) LUC is quantified, and disparities in data availability and quality. The lack of thorough sensitivity and uncertainty analysis hinders the evaluation of plausible ranges of estimates of GHG emissions from LUC. The relatively limited fuel coverage in the literature precludes a complete set of direct comparisons across alternative and conventional fuels sought by regulatory bodies and researchers.

Improved modeling approaches, consistent definitions and classifications, availability of high‐resolution data on LUC over time, development of standardized reference and future scenarios, incorporation of non‐economic drivers of LUC, and more rigorous treatment of uncertainty can help improve LUC estimates in effectively achieving policy goals. © 2013 Society of Chemical Industry and John Wiley & Sons, Ltd
Review of US and EU initiatives toward development, demonstration, and commercialization of lignocellulosic biofuels
Authors: Balan Venkatesh , Chiaramonti David , Kumar Sandeep
Published: August 2013

Advanced biofuels produced from lignocellulosic biomass offer an exciting opportunity to produce renewable liquid transportation fuels, biochemicals, and electricity from locally available agriculture and forest residues. The growing interest in biofuels from lignocellulosic feedstock in the United States (US) and the European Union (EU) can provide a path forward toward replacing petroleum‐based fuels with sustainable biofuels which have the potential to lower greenhouse gas (GHG) emissions. The selection of biomass conversion technologies along with feedstock development plays a crucial role in the commercialization of next‐generation biofuels. There has been synergy and, even with similar basic process routes, diversity in the conversion technologies chosen for commercialization in the EU and the US. The conversion technologies for lignocellulosic biomass to advanced biofuels can be broadly classified in three major categories: biochemical, thermochemical, and hybrid conversions. The objective of this review is to discuss the US and EU biofuel initiatives, feedstock availability, and the state‐of‐art conversion technologies that are potentially ready or are already being deployed for large‐scale applications. The review covers and compares the developments in these areas in the EU and the USA and provides a comprehensive list of the most relevant ongoing development, demonstration, and commercialization activities in various companies, along with the different processing strategies adopted by these projects. © 2013 The Authors. Biofuels, Bioproducts, Biorefining published by Society of Chemical Industry and John Wiley & Sons, Ltd.
Pulsradiolytische Untersuchung der Oxidation von ungesättigten Karbonylverbindungen in wäßriger Lösung: Hydratisierte Enole als Zwischenprodukte
Authors: Lilie J. , Henglein A.
Published: August 2013

Das OH‐Radikal lagert sich diffusions‐kontrolliert an die Doppelbindungen von Vinylmethylketon, Acrolein und Crotonaldehyd an. Die Spektren der gebildeten C. Radikale wurden gemessen. Die aus Vinylmethylketon und Acrolein gebildeten Radikale disproportionieren mit 30% Häufigkeit, wobei die Enole des Acetoacetaldehyds bzw. des Malondialdehyds entstehen. Die aus Crotonaldehyd gebildeten Radikale disproportionieren mit 86% Häufigkeit, wobei das Enol des Acetoacetaldehyds entsteht.

Wenn das OH‐Radikal sich an die hydratisierte Form des Crotonaldehyds anlagert, entsteht letztlich das hydratisierte Enol des Acetoacetaldehyds. Die Geschwindigkeitskonstante der spontanen Dehydratation dieses Teilchens

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wurde zu 54s−1 bestimmt. Die Dehydratation wird durch OH− ‐Ionen in alkalischer Lösung katalysiert. Der pK‐Wert des hydratisierten Enols wurde zu pK = 11,6 bestimmt, die Geschwindigkeitskonstante der spontanen Dehydratation des hydratisierten Enol‐Anions

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zu 1,0·104s−1. Die Geschwindigkeitskonstante und Aktivierungsenergie der spontanen Dehydratation des Enols des Malondialdehyds betragen 40s−1 (bei 20°C) bzw. 7,7kcal/mol.
Thermodynamics of metal/hydrogen systems
Authors: Flanagan Ted B. , Oates W. A.
Published: August 2013

The thermodynamics of metal/hydrogen systems are reviewed. Emphasis is placed on the thermodynamic properties of hydrogen dissolved in single solid phase regions. Methods of investigation are discussed. A brief survey of recent results on binary metal alloy/hydrogen systems is presented.
Multivariate frailty models for two types of recurrent events with a dependent terminal event: Application to breast cancer data
Authors: Mazroui Yassin , Mathoulin‐Pélissier Simone , MacGrogan Gaetan , Brouste Véronique , Rondeau Virginie
Published: August 2013

Individuals may experience more than one type of recurrent event and a terminal event during the life course of a disease. Follow‐up may be interrupted for several reasons, including the end of a study, or patients lost to follow‐up, which are noninformative censoring events. Death could also stop the follow‐up, hence, it is considered as a dependent terminal event. We propose a multivariate frailty model that jointly analyzes two types of recurrent events with a dependent terminal event. Two estimation methods are proposed: a semiparametrical approach using penalized likelihood estimation where baseline hazard functions are approximated by M‐splines, and another one with piecewise constant baseline hazard functions. Finally, we derived martingale residuals to check the goodness‐of‐fit. We illustrate our proposals with a real dataset on breast cancer. The main objective was to model the dependency between the two types of recurrent events (locoregional and metastatic) and the terminal event (death) after a breast cancer.
Metabolic syndrome does not impact long‐term survival in patients with acute myocardial infarction after successful percutaneous coronary intervention with drug‐eluting stents
Authors: Won Ki‐Bum , Kim Byeong‐Keuk , Chang Hyuk‐Jae , Shin Dong‐Ho , Kim Jung‐Sun , Ko Young‐Guk , Choi Donghoon , Ha Jong‐Won , Hong Myeong‐Ki , Jang Yangsoo
Published: August 2013

Objective

This study aimed to evaluate long‐term survival according to the presence of metabolic syndrome (MS) in patients with acute myocardial infarction (AMI) undergoing successful percutaneous coronary intervention (PCI) with drug‐eluting stents (DES).

Background

Despite the significance of coronary reperfusion in AMI, the prognostic impact of MS has been investigated under inconsistent reperfusion therapy in AMI patients.

Methods and Results

Three‐year clinical outcomes, including all‐cause death and the composite of cardiac death or myocardial infarction, were evaluated according to MS status for 963 patients with AMI treated with successful PCI with DES. This study included 494 subjects with MS (51%) and 469 subjects without MS (49%). The incidence of multivessel disease and the mean number of implanted stents were significantly higher in patients with MS than in patients with non‐MS. The occurrence of all‐cause death (5.9% vs. 6.4%, P = 0.789) and the composite outcomes (5.1% vs. 6.2%, P = 0.485) did not differ significantly between patients with and without MS. Cox regression models revealed that MS had no significant impact on all‐cause death (hazard ratio [HR] 0.91; 95% confidence interval [CI] 0.55–1.52; P = 0.726) or the composite outcomes (HR 0.81; 95% CI 0.48–1.39; P = 0.448). Obesity was associated with a decreased risk of all‐cause death and the composite outcomes among all MS components.

Conclusions

No difference was observed in long‐term survival according to the presence of MS in patients with AMI after successful PCI with DES. This suggests that reperfusion therapy using PCI with DES is equally beneficial in patients AMI with and without MS. © 2013 Wiley Periodicals, Inc.
First human experience of thermal arterial closure
Authors: Davidson Laura J. , Luna Jorge , Virmani Renu , Asscher Jacqueline A. , Davidson Charles J.
Published: August 2013

Objectives: This study was designed to evaluate the efficacy and safety of the CardioDex arterial closure device, which is a novel femoral artery closure device used following percutaneous cardiac catheterization. Background: Current devices utilized to achieve hemostasis of the femoral artery following percutaneous cardiac catheterization include collagen plug and suture mediated devices, but are associated with significant vascular complications. The CardioDex closure device utilizes thermal energy to cause collagen shrinking and swelling and thereby, achieve hemostasis. Methods: The device was evaluated in a prospective nonrandomized single‐center trial with patients undergoing 6F invasive cardiac procedures. Femoral artery puncture closure was performed immediately at completion of the procedure, followed by 3–4 minutes of manual compression. Time to hemostasis (TTH), time to ambulation (TTA), and short‐term clinical follow‐up data were collected. Results: A total of 34 patients including 21 diagnostic and 13 interventional cases were evaluated. The median TTH was 3 min in diagnostic and 4 min in interventional cases. TTH was independent of activated clotting time (ACT). The median TTA was 2.75 hr and 3.37 hr in diagnostic and interventional groups, respectively. There were no major adverse events identified at 1 week and 30 day follow up. Conclusions: This first in human clinical experience with the CardioDex closure device demonstrates that in the small cohort studied, it is safe and effective in diagnostic cardiac catheterization and also in interventional cases on mild anticoagulation (mean ACT = 188 sec). It has the advantage of leaving no foreign material in the body following use. © 2013 Wiley Periodicals, Inc.
Volume‐to‐creatinine clearance ratio in patients undergoing coronary angiography with or without percutaneous coronary intervention: Implications of varying definitions of contrast‐induced nephropathy
Authors: Capodanno Davide , Ministeri Margherita , Cumbo Silvia , Dalessandro Veronica , Tamburino Corrado
Published: August 2013

Objectives

Whether predicting the risk of early serum creatinine rise using the ratio of the volume of contrast media administered to the estimated creatinine clearance (V/CrCl) is applicable to the broader definition of contrast‐induced nephropathy (CIN) (≥0.5 mg/dL absolute and/or 25% relative increase from baseline serum creatinine) is unknown.

Background

A V/CrCl ≥4 has been proven to predict the risk of ≥0.5 mg/dL postprocedural absolute rise in serum creatinine.

Methods

A total of 722 patients undergoing coronary angiography ± percutaneous coronary intervention (PCI) between March 2011 and October 2011 with paired serum creatinine determinations at preprocedure and within 72‐hr postprocedure were analyzed. The V/CrCl ratio was calculated by dividing the volume of contrast received by the patient's creatinine clearance. CIN using different definitions was termed as CINnarrow (rise in serum creatinine ≥0.5 mg/dL) and CINbroad (rise in serum creatinine ≥0.5 mg/dL and/or ≥25% increase in baseline serum creatinine).

Results

The mean age was 66 ± 11 years and the mean baseline serum creatinine was 1.1 ± 0.8 mg/dL. Patients with V/CrCl ≥4 were significantly older and more frequently underwent ad hoc PCI compared with those with V/CrCl <4. CINnarrow and CINbroad were observed in 13 versus 3% (P < 0.001) and 23 versus 11% (P < 0.001) of patients with or without V/CrCl ≥4, respectively. After statistical adjustment, a V/CrCl ratio ≥4 remained significantly associated with the risk of both CINnarrow [adjusted OR 3.5, 95% confidence intervals (95% CI) 1.7–7.3; P < 0.001] and CINbroad (adjusted OR 2.5, 95% 1.6–3.9; P < 0.001).

Conclusions

A volume‐to‐creatinine clearance ratio ≥4 significantly predicts the risk of early postprocedural rise in serum creatinine regardless of the CIN definition adopted. © 2013 Wiley Periodicals, Inc.
Phosphate‐Doped Carbon Black as Pt Catalyst Support: Co‐catalytic Functionality for Dimethyl Ether and Methanol Electro‐oxidation
Authors: Yin Min , Huang Yunjie , Li Qingfeng , Jensen Jens Oluf , Cleemann Lars N. , Zhang Wei , Bjerrum Niels J. , Xing Wei
Published: August 2013

Niobium‐phosphate‐doped (NbP‐doped) carbon blacks were prepared as the composite catalyst support for Pt nanoparticles. Functionalities of the composite include intrinsic proton conductivity, surface acidity, and interfacial synergistic interactions with methanol and dimethyl ether (DME). The supported Pt catalysts show significant improvement in catalytic activity towards the direct oxidation of methanol and DME, attributable to the enhanced adsorption and dehydrogenation of methanol and DME, as well as the presence of activated OH species in the catalysts. The latter is demonstrated to facilitate the removal of CO intermediates formed during the oxidation reactions.
General Synthesis and Physicochemical Characterisation of a Series of Peptide‐Mimic Lysine‐Based Amino‐Functionalised Lipids
Authors: Wölk Christian , Drescher Simon , Meister Annette , Blume Alfred , Langner Andreas , Dobner Bodo
Published: August 2013

A series of novel malonic acid diamides (second generation) with two long hydrophobic alkyl chains and an alkaline polar head group was synthesised and characterised as a new class of amino‐functionalised lipids. These peptide‐mimic lipids are suitable for polynucleotide transfer. The lipids bear a novel backbone consisting of a lysine unit and a malonic acid unit. Six different head‐group structures, which vary in size and number of amino groups that can be protonated, were attached to the backbone structure. Furthermore, different alkyl chains were used to build the lipophilic part (namely tetradecyl, hexadecyl, and oleyl). Phase transitions of the new compounds in aqueous dispersions at pH 10 were analysed and discussed in terms of head group and alkyl chain variations. The shape and size of the formed aggregates of selected lipid dispersions were investigated by dynamic light scattering and transmission electron microscopy.
Conductive, Monodisperse Polyaniline Nanofibers of Controlled Length Using Well‐Defined Cylindrical Block Copolymer Micelles as Templates
Authors: McGrath Nina , Patil Avinash J. , Watson Scott M. D. , Horrocks Benjamin R. , Faul Charl F. J. , Houlton Andrew , Winnik Mitchell A. , Mann Stephen , Manners Ian
Published: August 2013

Stable colloidal dispersions of polyaniline (PAni) nanofibers with controlled lengths from about 200 nm–1.1 μm and narrow length distributions (Lw/Ln<1.04; Lw=weight average micelle length, Ln=number average micelle length) were prepared through the template‐directed synthesis of PAni using monodisperse, solution‐self‐assembled, cylindrical, block copolymer micelles as nanoscale templates. These micelles were prepared through a crystallization‐driven living self‐assembly method from a poly(ferrocenyldimethylsilane)‐b‐poly(2‐vinylpyridine) block copolymer (PFS25‐b‐P2VP425). This material was initially self‐assembled in iPrOH to form cylindrical micelles with a crystalline PFS core and a P2VP corona and lengths of up to several micrometers. Sonication of this sample then yielded short cylinders with average lengths of 90 nm and a broad length distribution (Lw/Ln=1.32). Cylindrical micelles of PFS25‐b‐P2VP425 with controlled lengths and narrow length distributions (Lw/Ln<1.04) were subsequently prepared using thermal treatment at specific temperatures between 83.5 and 92.0 °C using a 1D self‐seeding process. These samples were then employed in the template‐directed synthesis of PAni nanofibers through a two‐step procedure, where the micellar template was initially stabilised by deposition of an oligoaniline coating followed by addition of a polymeric acid dopant, resulting in PAni nanofibers in the emeraldine salt (ES) state. The ES–PAni nanofibers were shown to be conductive by scanning conductance microscopy, whereas the precursor PFS25‐b‐P2VP425 micelle templates were found to be dielectric in character.
Tuning the Dispersibility of Carbon Nanostructures from Organophilic to Hydrophilic: Towards the Preparation of New Multipurpose Carbon‐Based Hybrids
Authors: Georgakilas Vasilios , Kouloumpis Antonios , Gournis Dimitrios , Bourlinos Athanasios , Trapalis Christos , Zboril Radek
Published: August 2013

The hydroxyphenyl derivatives of carbon nanostructures (graphene and carbon nanotubes) can be easily transformed into highly organophilic or hydrophilic derivatives by using the ionic interactions between the phenolic groups and oleylamine or tetramethylammonium hydroxide, respectively. The products were finely dispersed in homo‐polymers or block co‐polymers to create homogeneous carbon‐based nanocomposites and were used as nanocarriers for the dispersion and protection of strongly hydrophobic compounds, such as large aromatic chromophores or anticancer drugs in aqueous solutions.
High Charge Delocalization and Conjugation in Oligofuran Molecular Wires
Authors: Gidron Ori , Diskin‐Posner Yael , Bendikov Michael
Published: August 2013

The extent of charge delocalization and of conjugation in oligofurans and oligothiophenes was studied by using mixed valence systems comprising oligofurans and oligothiophenes capped at both ends by ferrocenyl redox units. Using electrochemical, spectral, and computational tools, we find strong charge delocalization in ferrocene‐capped oligofurans which was stronger than in the corresponding oligothiophene systems. Spectroscopic studies suggest that the electronic coupling integral (Hab) is roughly 30–50 % greater for oligofuran‐bridged systems, indicating better energy matching between ferrocene units and oligofurans. The distance decay constant (damping factor), β, is similar for oligofurans (0.066 A−1) and oligothiophenes (0.070 A−1), which suggests a similar extent of delocalization in the bridge, despite the higher HOMO–LUMO gap in oligofurans. Computational studies indicate a slightly larger extent of delocalization in furan‐bridged systems compared with thiophene‐bridged systems, which is consistent with oligofurans being significantly more rigid and less aromatic than oligothiophenes. High charge delocalization in oligofurans, combined with the previously reported strong fluorescence, high mobility, and high rigidity of oligofuran‐based materials makes them attractive candidates for organic electronic applications.
Nanosilver‐Decorated TiO2 Nanofibers Coated with a SiO2 Layer for Enhanced Light Scattering and Localized Surface Plasmons in Dye‐Sensitized Solar Cells
Authors: Hwang Sun Hye , Roh Jongmin , Jang Jyongsik
Published: August 2013

Enhanced harvesting of visible light is vital to the development of highly efficient dye‐sensitized solar cells (DSSCs). Nanosilver‐decorated TiO2 nanofibers (Ag@TiO2 NFs) were synthesized by depositing chemically reduced Ag ions onto the surface of electrospun TiO2 nanofibers (TiO2 NFs). The prepared Ag@TiO2 NFs were coated with SiO2 (SiO2@Ag@TiO2 NFs) by using PVP as coupling agent for protecting corrosion of Ag nanoparticle by I−/${{\rm I}{{- \hfill \atop 3\hfill}}}$ solution. The fabricated SiO2@Ag@TiO2 NFs demonstrated a synergistic effect of light scattering and surface plasmons, leading to an enhanced light absorption. Moreover, an anode consisting of SiO2@Ag@TiO2 NFs incorporating TiO2 nanoparticles (NPs) increased light harvesting without substantially sacrificing dye attachment. The power conversion efficiency increased from 6.8 to 8.7 % for a thick film (10 μm), that is, 28 %. These results suggest that SiO2@Ag@TiO2 NFs are promising materials for enhanced light absorption in dye‐sensitized solar cells.
Cyclometalation of Aryl‐Substituted Phosphinines through CH‐Bond Activation: A Mechanistic Investigation
Authors: Broeckx Leen E. E. , Güven Sabriye , Heutz Frank J. L. , Lutz Martin , Vogt Dieter , Müller Christian
Published: August 2013

A series of 2,4,6‐triarylphosphinines were prepared and investigated in the base‐assisted cyclometalation reaction using [Cp*IrCl2]2 (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) as the metal precursor. Insight in the mechanism of the CH bond activation of phosphinines as well as in the regioselectivity of the reaction was obtained by time‐dependent 31P{1H} NMR spectroscopy. At room temperature, 2,4,6‐triarylphosphinines instantaneously open the Ir‐dimer and coordinate in an η1‐fashion to the metal center. Upon heating, a dissociation step towards free ligand and an Ir‐acetate species is observed and proven to be a first‐order reaction with an activation energy of ΔEA=56.6 kJ mol−1 found for 2,4,6‐triphenylphosphinine. Electron‐donating substituents on the ortho‐phenyl groups of the phosphorus heterocycle facilitate the subsequent cyclometalation reaction, indicating an electrophilic CH activation mechanism. The cyclometalation reaction turned out to be very sensitive to steric effects as even small substituents can have a large effect on the regioselectivity of the reaction. The cyclometalated products were characterized by means of NMR spectroscopy and in several cases by single‐crystal X‐ray diffraction. Based on the observed trends during the mechanistic investigation, a concerted base‐assisted metalation–deprotonation (CMD) mechanism, which is electrophilic in nature, is proposed.
Use of Cleavable Coordinating Rings as Protective Groups in the Synthesis of a Rotaxane with an Axis that Incorporates More Chelating Groups Than Threaded Macrocycles
Authors: Joosten Antoine , Trolez Yann , Heitz Valérie , Sauvage Jean‐Pierre
Published: August 2013

A new methodology allowing preparation of a linear “unsaturated” [3]rotaxane consisting of an axis incorporating more coordination sites than threaded rings was developed. It was based on the preliminary synthesis of a “saturated” [5]rotaxane consisting of a four‐chelating site axis threaded through four macrocyclic components, two of them being cleavable rings incorporating a lactone function and the two others being “secure” non‐cleavable rings. The stoppering reaction was based on click chemistry. Subsequently, cleavage and removal of the two lactone‐containing macrocycles from the [5]rotaxane in basic medium afforded the desired “unsaturated” [3]rotaxane in quantitative yield.
Benzofurazane as a New Redox Label for Electrochemical Detection of DNA: Towards Multipotential Redox Coding of DNA Bases
Authors: Balintová Jana , Plucnara Medard , Vidláková Pavlína , Pohl Radek , Havran Luděk , Fojta Miroslav , Hocek Michal
Published: August 2013

Benzofurazane has been attached to nucleosides and dNTPs, either directly or through an acetylene linker, as a new redox label for electrochemical analysis of nucleotide sequences. Primer extension incorporation of the benzofurazane‐modified dNTPs by polymerases has been developed for the construction of labeled oligonucleotide probes. In combination with nitrophenyl and aminophenyl labels, we have successfully developed a three‐potential coding of DNA bases and have explored the relevant electrochemical potentials. The combination of benzofurazane and nitrophenyl reducible labels has proved to be excellent for ratiometric analysis of nucleotide sequences and is suitable for bioanalytical applications.
Tandem Synthesis of Benzo[b]carbazoles and Their Photoluminescent Properties
Authors: Xing Yanpeng , Hu Binbin , Yao Qijun , Lu Ping , Wang Yanguang
Published: August 2013

5 H‐Benzo[b]carbazoles were prepared through a tandem reaction between 2‐ethynyl‐N‐triphenylphosphoranylidene anilines and α‐diazoketones through ketenimine intermediates in moderate‐to‐good yields. By using this approach, benzo[b]benzo[5,6]indolo[3,2‐h]carbazoles, fluoreno[9,1‐ab]carbazoles, and fluoreno[9,1‐ab]fluoreno[1′,9′:5,6,7]indolo[3,2‐h]carbazoles were constructed in one pot. Moreover, the resulting products emitted light within the range 410–521 nm, with quantum yields of up to 62 %.
A Unique Au–Ag–Au Triangular Motif in a Trimetallic Halonium Dication: Silver Incorporation in a Gold(I) Catalyst
Authors: Zhu Yuyang , Day Cynthia S. , Zhang Lin , Hauser Katarina J. , Jones Amanda C.
Published: August 2013

As a result of explorations into the solution chemistry of silver/gold mixtures, a unique diphosphine trimetallic chloronium dication was discovered that incorporates silver–arene chelation and a triangular mixed gold/silver core in the solid state. Notably, it was isolated from a Celite prefiltered solution initially thought to be silver‐free. The crystal structure also incorporates the coordination to silver of one fluorine atom of one SbF6− counterion. The structure was compared to two new, but well‐precedented, phosphine digold chloride cations. DFT calculations supported significant silver–halide and silver–arene interactions in the mixed gold/silver complex and metallophilic interactions in all three complexes. Comparison of computed data revealed that the ωB97X‐D functional, which has a long‐range corrected hybrid with atom–atom dispersion corrections, gave a better fit to the experimental data compared with the PBE0 functional, which has previously failed to capture aurophilic interactions. Preliminary studies support the presence of the mixed gold/silver structure in solution.
Effects of the 2011 Tohoku‐Oki M9.0 Earthquake on the Crustal Movement in the Shandong Area Derived from GPS Data
Authors: Hai‐Tao YIN , Wei‐Jun GAN , Bei HUANG , Gen‐Ru XIAO , Jie LI , Cheng‐Lin ZHU
Published: August 2013

Based on the Shandong Crustal Movement GPS Observation Network, combining the global GPS data provided by IGS, we calculate the effects of 2011 Tohoku‐Oki M9.0 earthquake on the Shandong area and obtain the real motion tracks of stations in this region. The results show that: the maximum amplitude is more than 0.2 m at the GPS stations in Shandong during the earthquake, the wave movement lasted about 160 s. The direction of co‐seismic displacement is nearly south‐easterly, and the maximum displacement exceeds 10 mm. The effect of this earthquake on the Shandong area is dominated by horizontal displacement, posing a tension on the Yishu fault zone, on which the tension amplitude of the northern part is obviously larger than the southern part. From the recent movement trend of GPS stations, the blocks of the Shandong area are moving back to west. So we speculate that the movement pattern will return to the former state in about 3∼5 month after the earthquake. This would be of significance for earthquake monitoring in this area.
SaC/C formulations of the all‐pairs N‐body problem and their performance on SMPs and GPGPUs
Authors: Šinkarovs Artjoms , Scholz Sven‐Bodo , Bernecky Robert , Douma Roeland , Grelck Clemens
Published: August 2013

This paper describes our experience in implementing the classical N‐body algorithm in SaC and analysing the runtime performance achieved on three different machines: a dual‐processor 8‐core Dell PowerEdge 2950 (a Beowulf cluster node, the reference machine), a quad‐core hyper‐threaded Intel Core‐i7 based system equipped with an NVidia GTX‐480 graphics accelerator and an Oracle Sparc T4‐4 server with a total of 256 hardware threads. We contrast our findings with those resulting from the reference C code and a few variants of it that employ OpenMP pragmas as well as explicit vectorisation. Our experiments demonstrate that the SaC implementation successfully combines a high level of abstraction, very close to the mathematical specification, with very competitive runtimes. In fact, SaC matches or outperforms the hand‐vectorised and hand‐parallelised C codes on all three systems under investigation without the need for any source code modification. Furthermore, only SaC is able to effectively harness the advanced compute power of the graphics accelerator, again by mere recompilation of the same source code. Our results illustrate the benefits that SaC provides to application programmers in terms of coding productivity, source code, and performance portability among different machine architectures, as well as long‐term maintainability in evolving hardware environments. Copyright © 2013 John Wiley & Sons, Ltd.
Functional development of γδ T cells
Authors: Prinz Immo , Silva‐Santos Bruno , Pennington Daniel J.
Published: August 2013

The thymus generates T cells that are generally functionally immature and thus require peripheral activation for differentiation into effector lymphocytes. Notable exceptions to this rule are murine γδ T cells, many of which have been shown to acquire their functional potential during thymic development from late embryonic stages. Here, we review the underlying ontogenic processes and molecular differentiation mechanisms of murine γδ T cells, focusing on the transcriptional control of IFN‐γ and IL‐17 expression. We propose that functional commitment of γδ T cells occurs in “developmental windows” defined by the molecular composition of the thymic microenvironment, such as T‐cell receptor (TCR), TCR coreceptor ligands, and cytokines. We further discuss the similarities and particularities of functional development of γδ T cells in mice and humans, while highlighting some key unresolved issues for future investigation.
Damage control: Management of cellular stress by the NLRP3 inflammasome
Authors: Haasken Stefanie , Sutterwala Fayyaz S.
Published: August 2013

The NLRP3 inflammasome plays a critical role in regulating inflammatory and cell death pathways in response to a diverse array of stimuli. Activation of the NLRP3 inflammasome results in activation of the cysteine protease caspase‐1 and the subsequent processing and secretion of the proinflammatory cytokines IL‐1β and IL‐18. In this issue of the European Journal of Immunology, Licandro et al. [Eur. J. Immunol. 2013. 43, 2126–2137] show that the NLRP3 inflammasome contributes to oxidative DNA damage. In addition, activation of the NLRP3 inflammasome modulates a number of pathways involved in DNA damage repair, cell cycle, and apoptosis, suggesting a novel role for the NLRP3 inflammasome in DNA damage responses following cellular stress.
Thermally Induced Dehydrogenation of Amine–Borane Adducts and Ammonia–Borane by Group 6 Cyclopentadienyl Complexes Having Single and Triple ­Metal–Metal Bonds
Authors: García‐Vivó Daniel , Huergo Estefanía , Ruiz Miguel A. , Travieso‐Puente Raquel
Published: August 2013

Treatment of solutions of ammonia–borane (NH3·BH3, AB) with catalytic amounts (5 mol‐%) of the singly bonded dimers [M2Cp2(CO)6] [M = Cr (1a), Mo (1b), W (1c); Cp = cyclopentadienyl] under mild thermal activation (333 K) led to the progressive dehydrogenation of the adduct and quantitative conversions were achieved after 12, 24, and >34 h, respectively. At the initial stages of these reactions (low conversions), the major products were cyclic and branched oligomers of aminoborane (NH2=BH2). However, at longer reaction times (high conversions), the major products were, in all cases, borazine, [HNBH]3, and polyborazylene, [NBHx] (x < 1), whereas other minor products were derived from B–N bond‐cleavage processes. Over the course of these reactions, complexes 1a–c were transformed into the corresponding mononuclear hydrides [MCpH(CO)3] [M = Cr (2a), Mo (2b), W (2c)], which are supposed to be the catalytically active species in these processes, as also supported by similar catalytic activity exhibited by pure samples of the dihydride [Mo2Cp2(H)2(μ‐Ph2PCH2PPh2)(CO)2] (2b′). Under similar conditions, 1a–c were also active catalysts for the dehydrogenation of adducts derived from substituted amines (tBuH2N·BH3 and Me2HN·BH3), although the rate of dehydrogenation was significantly lower than that of AB. This lower activity follows from deprotonation of hydrides 2 by the free amines, which are in turn generated through B–N bond‐cleavage processes. The dehydrogenation products of tBuH2N·BH3 are also derived from oligomerization processes of the corresponding aminoborane (tBuHN=BH2), which in this case was identified in the reaction mixtures, but even at long reaction times, the formation of the borazine‐like product was not complete, and the reaction mixture contained significant amounts of (poorly defined) soluble polymeric materials. For Me2HN·BH3, the major product obtained in all of the reactions was cyclic dimer [Me2N=BH2]2. Similar studies were performed with triply bonded complexes [Mo2Cp2(CO)4] (3b) and [Mo2Cp2(μ‐Ph2PCH2PPh2)(CO)2] (3b′), which displayed similar catalytic activity while remaining essentially unperturbed along the reactions, and these complexes yielded product distributions that were similar to those observed for singly bonded dimers 1a–c.
An Approach to the Synthesis of Functionalized Polycyclic Aromatic Hydrocarbons
Authors: Little Mark , Lan He , Raftery James , Morrison John J. , McDouall Joseph J. W. , Yeates Stephen G. , Quayle Peter
Published: August 2013

The application of a new benzannulation reaction for the regiocontrolled synthesis of functionalized chrysenes is reported. The initial benzannulation and the subsequent halogen displacement reactions are both highly regiospecific, which thereby enables the regiocontrolled synthesis of a variety of 4,10‐disubstituted chrysenes from commercially available 1,5‐dihydroxynaphthalene.
A Comparison of the Gas‐Product‐Release Characteristics from Coal Pyrolysis and Hydrogasification
Authors: Hong Bingqing , Wang Xingjun , Zhou Zhijie , Yu Guangsuo
Published: August 2013

Coal pyrolysis and hydrogasification were investigated in a laboratory‐scale pressurized fixed‐bed reactor to examine the effects of temperature, pressure, and catalyst on the gas productivity and yields under different gas atmospheres. The experimental results show that the methane yield is significantly higher under a hydrogen atmosphere. The release rate curve of methane during hydrogasification has three obvious peaks which are the results of coal devolatilization and rapid hydrogenation, the secondary reaction of volatile products, and the slow hydrogenation of residual char, respectively, whereas that of pyrolysis only exhibits the first peak. Changes in temperature and pressure have more remarkable effects on coal hydrogasification than on pyrolysis. Nickel and calcium‐based catalysts influence the rate of CO and CO2 formation but little effect was observed on low‐carbon hydrocarbon production. Potassium‐ and sodium‐based catalysts have a significant effect on the formation of methane under a hydrogen atmosphere. The FTIR spectra show that hydrogen is easily bound to carbon if of potassium‐ and sodium‐based catalysts are used, and CC bond formation is inhibited, which reduces the aggregation of graphite which has very poor activity. Therefore, potassium‐ and sodium‐catalyzed samples could maintain high activities during hydrogasification.
PCDH10 promoter hypermethylation is frequent in most histologic subtypes of mature lymphoid malignancies and occurs early in lymphomagenesis
Authors: Narayan Gopeshwar , Xie Dongxu , Freddy Allen J. , Ishdorj Ganchimeg , Do Catherine , Satwani Prakash , Liyanage Hema , Clark Lorraine , Kisselev Sergey , Nandula Subhadra V. , Scotto Luigi , Alobeid Bachir , Savage David , Tycko Benjamin , O'Connor Owen A. , Bhagat Govind , Murty Vundavalli V.
Published: August 2013

PCDH10 is epigenetically inactivated in multiple tumor types; however, studies in mature lymphoid malignancies are limited. Here, we have investigated the presence of promoter hypermethylation of the PCDH10 gene in a large cohort of well‐characterized subsets of lymphomas. PCDH10 promoter hypermethylation was identified by methylation‐specific PCR in 57 to 100% of both primary B‐ and T‐cell lymphoma specimens and cell lines. These findings were further validated by Sequenom Mass‐array analysis. Promoter hypermethylation was also identified in 28.6% cases of reactive follicular hyperplasia, more commonly occurring in states of immune deregulation and associated with rare presence of clonal karyotypic aberrations, suggesting that PCDH10 methylation occurs early in lymphomagenesis. PCDH10 expression was down regulated via promoter hypermethylation in T‐ and B‐cell lymphoma cell lines. The transcriptional down‐regulation resulting from PCDH10 methylation could be restored by pharmacologic inhibition of DNA methyltransferases in cell lines. Both T‐ and B‐cell lymphoma cell lines harboring methylation‐mediated inactivation of PCDH10 were resistant to doxorubicin treatment, suggesting that hypermethylation of this gene might contribute to chemotherapy response. © 2013 Wiley Periodicals, Inc.
Upper Cretaceous marine‐continental transition (Leonese Area, NW Spain) defined from integrated outcrop and seismic stratigraphy
Authors: Herrero‐Hernández Antonio , Gómez‐Fernández Fernando , López‐Moro Francisco Javier
Published: August 2013

The Upper Cretaceous succession of the Leonese Area (NW Spain) comprises mixed clastic and carbonate sediments. This succession is divided into two lithostratigraphic units, the Voznuevo Member and the Boñar Formation, which represent fluvial, shoreface, intertidal, subtidal and open‐shelf sedimentary environments. Regional seismic interpretation and sequence stratigraphic analysis have allowed the study of lateral and vertical changes in the sedimentary record and the definition of third‐order levels of stratigraphic cyclicity. On the basis of these data, the succession can be divided into two second‐order depositional sequences (DS‐1 and DS‐2), incorporating three system tracts in a lowstand to transgressive to highstand system tract succession (LST–TST–HST). These sequences are composed of fluvial systems at the base with palaeocurrents that flowed westward and south‐westward. The upper part of DS‐1 (Late Albian–Middle Turonian) shows evidence of intertidal to subtidal and offshore deposits. DS‐2 (Late Turonian–Campanian) comprises intertidal to subtidal, tidal flat, shallow marine and lacustrine deposits and interbedded fluvial deposits. Two regressive–transgressive cycles occurred in the area related to eustatic controls. The evolution of the basin can be explained by base‐level changes and associated shifts in depositional trends of successive retrogradational episodes. By using isobath and isopach maps, the main palaeogeographic features of DS‐1 and DS‐2 were constrained, namely coastline positions, the existence and orientation of corridors through which fluvial networks were channelled and the location of the main depocentres of the basin. Sedimentation on the Upper Cretaceous marine platform was mainly controlled by (i) oscillations of sea level and (ii) the orientation of Mesozoic faults, which induced sedimentation along depocentres. Copyright © 2013 John Wiley & Sons, Ltd.
Therapeutic immunization and local low‐dose tumor irradiation, a reinforcing combination
Authors: Draghiciu Oana , Walczak Mateusz , Hoogeboom Baukje Nynke , Franken Kees L.M.C. , Melief Kees J.M. , Nijman Hans W. , Daemen Toos
Published: August 2013

Therapeutic cancer vaccines show promise in preclinical studies, yet their clinical efficacy is limited. Increased recruitment of immune cells into tumors and suppression of the immune suppressive tumor environment are critical components toward effective cancer immunotherapies. Here, we report how local low‐dose irradiation, alone or with a therapeutic immunization based on Semliki Forest virus (SFV) against human papillomavirus (HPV)‐related cancer, influences these immune mechanisms. We first demonstrated that immunization with SFVeE6,7 or SFVeOVA, replicon particles expressing either HPV16 E6/E7 or ovalbumin, resulted in an antigen‐specific migration of CD8+ T cells into HPV‐ and OVA‐specific tumors. Local low‐dose tumor irradiation alone resulted in a 2‐fold increase of intratumoral CD8+ T cells. When 14 Gy irradiation was combined with immunization, intratumoral numbers of CD8+ T cells increased 10‐fold and the number of CD8+ T cells specific for the E7‐ epitope increased more than 20‐fold. Irradiation alone however also increased the number of intratumoral myeloid‐derived suppressor cells (MDSCs) 3.5‐fold. Importantly, this number did not further increase when combined with immunization. As a result, the ratio of antigen‐specific CD8+ T cells and MDSCs in tumors increased up to 85‐fold compared to the control. We furthermore demonstrated that following irradiation CCR2 and CCL2, CXCR6 and CCL16, chemokines and ligands involved in tumor homing of immune cells, were significantly up regulated. This study demonstrates that local low‐dose tumor irradiation influences the intratumoral immune population induced by SFVeE6,7 immunization by a strong increase in the ratio of antitumoral to immune suppressive cells, thus changing the intratumoral immune balance in favor of antitumor activity.
Alcohol and smoking and subsequent risk of prostate cancer in Japanese men: The Japan Public Health Center‐based prospective study
Authors: Sawada Norie , Inoue Manami , Iwasaki Motoki , Sasazuki Shizuka , Yamaji Taiki , Shimazu Taichi , Tsugane Shoichiro
Published: August 2013

Although alcohol and smoking have not been established as risk factors for prostate cancer, they are important risk factors for other human cancers and potentially major avoidable factors. Alcohol drinkers and smokers might be less likely to get screening, which might lead to attenuation of the positive association. Here, we investigated the association of alcohol drinking and smoking and prostate cancer according to stage, as well as prostate cancer detected by subjective symptoms, in a large prospective study among Japanese men. The Japan Public Health Center‐based prospective study (JPHC study) was established in 1990 for Cohort I and in 1993 for Cohort II. Subjects were 48,218 men aged 40–69 years who completed a questionnaire, which included their alcohol and smoking habits at baseline, and who were followed until the end of 2010. During 16 years of follow‐up, 913 men were newly diagnosed with prostate cancer; of whom 248 had advanced cases, 635 were organ‐localized and 30 were of an undetermined stage. Alcohol consumption was dose‐dependently associated with advanced prostate cancer [nondrinkers: reference, 0–150 g/week: hazard ratio (HR) = 1.23, 95% confidence interval (CI) = 0.83–1.82; 150–300 g/week: HR = 1.51, 95% CI = 1.04–2.19; ≥300 g/week: HR = 1.41, 95% CI = 0.97–2.05, p for trend = 0.02]. The positive association was not substantially changed among cancers detected by subjective symptoms. Smoking was inversely associated with prostate cancer among total subjects, but tended to increase the risk of advanced prostate cancer detected by subjective symptoms. In conclusion, abstinence from alcohol and prohibition of smoking might be important factors in the prevention of advanced prostate cancer.
Human papillomavirus prevalence and type distribution in invasive cervical cancer in sub‐Saharan Africa
Authors: Denny Lynette , Adewole Isaac , Anorlu Rose , Dreyer Greta , Moodley Manivasan , Smith Trudy , Snyman Leon , Wiredu Edwin , Molijn Anco , Quint Wim , Ramakrishnan Gunasekaran , Schmidt Johannes
Published: August 2013

In sub‐Saharan Africa, invasive cervical cancer (ICC) incidence and mortality are among the highest in the world. This cross‐sectional epidemiological study assessed human papillomavirus (HPV) prevalence and type distribution in women with ICC in Ghana, Nigeria, and South Africa. Cervical biopsy specimens were obtained from women aged ≥21 years with lesions clinically suggestive of ICC. Histopathological diagnosis of ICC was determined by light microscopy examination of hematoxylin and eosin stained sections of paraffin‐embedded cervical specimens; samples with a confirmed histopathological diagnosis underwent HPV DNA testing by polymerase chain reaction. HPV‐positive specimens were typed by reverse hybridization line probe assay. Between October 2007 and March 2010, cervical specimens from 659 women were collected (167 in Ghana, 192 in Nigeria and 300 in South Africa); 570 cases were histologically confirmed as ICC. The tumor type was identified in 551/570 women with ICC; squamous cell carcinoma was observed in 476/570 (83.5%) cases. The HPV‐positivity rate in ICC cases was 90.4% (515/570). In ICC cases with single HPV infection (447/515 [86.8%]), the most commonly detected HPV types were HPV16 (51.2%), HPV18 (17.2%), HPV35 (8.7%), HPV45 (7.4%), HPV33 (4.0%) and HPV52 (2.2%). The prevalence of single and multiple HPV infections seemed higher among HIV‐positive women and HPV type distribution appeared to differ according to tumor type and HIV status. In conclusion, HPV16, 18, 45 and 35 were the most common HPV types in sub‐Saharan African women with ICC and HPV infections were more common in HIV‐positive women.