bluuebunny/crossref_metadata_2025 huggingface dataset:
Precipitation characteristics of CAM5 physics at mesoscale resolution during MC3E and the impact of convective timescale choice
Authors: Gustafson William I. , Ma Po‐Lun , Singh Balwinder
Published: November 2014

The physics suite of the Community Atmosphere Model version 5 (CAM5) has recently been implemented in the Weather Research and Forecasting (WRF) model to explore the behavior of the parameterization suite at high resolution and within the controlled setting of a limited area model. The initial paper documenting this capability characterized the behavior for a northern high‐latitude region. This paper characterizes the precipitation characteristics for continental, midlatitude, springtime conditions during the Midlatitude Continental Convective Clouds Experiment (MC3E) over the central United States. This period exhibited a range of convective conditions from those driven strongly by large‐scale synoptic regimes to more locally driven convection. The study focuses on the precipitation behavior at 32 km grid spacing to better anticipate how the physics will behave in a global model when used at similar grid spacing in the coming years. Importantly, one change to the Zhang‐McFarlane deep convective parameterization when implemented in WRF was to make the convective timescale parameter an explicit function of grid spacing. This study examines the sensitivity of the precipitation to the default value of the convective timescale in WRF, which is 600 s for 32 km grid spacing, to the value of 3600 s used for 2° grid spacing in CAM5. For comparison, a 1200 s and an infinite convective timescale are also used. The results show that the 600 s timescale gives the most accurate precipitation amount over the central United States. However, this setting has the worst precipitation diurnal cycle, with the convection too tightly linked to the daytime surface heating. Longer timescales greatly improve the diurnal cycle but result in less precipitation and produce a low bias. An analysis of rain rates shows the accurate precipitation amount with the shorter timescale is assembled from an over abundance of drizzle combined with too few heavy rain events. With longer timescales, one can improve the frequency distribution, particularly for the extreme rain rates. Ultimately, without changing other aspects of the physics, one must decide between accurate diurnal timing and rain amount when choosing an appropriate convective timescale.
Plasmonic Particles that Hit Hypoxic Cells
Authors: Ratto Fulvio , Witort Ewa , Tatini Francesca , Centi Sonia , Lazzeri Lorenza , Carta Fabrizio , Lulli Matteo , Vullo Daniela , Fusi Franco , Supuran Claudiu T. , Scozzafava Andrea , Capaccioli Sergio , Pini Roberto
Published: November 2014

The use of gold nanorods as contrast agents for the optical hyperthermia of cancer is receiving ever more attention. However, their selective delivery to tumors still remains an outstanding problem. In most cases, the identification of suitable molecular targets is complicated by the lack of qualitative differences between healthy and cancer cells. The focus of prior work has mainly been on the cancer cells per se. Instead, here, the aim is moved to secondary fingerprints that arise in response to the cancer microenvironment. One common feature of tumors is a combination of poor oxygenation and high oxygen consumption, which generates hypoxia. Hypoxic cells need to switch to an anaerobic metabolism, which is accompanied by a multitude of molecular processes, including the expression of transmembrane isoforms of carbonic anhydrases. Here, gold nanorods are conjugated with selective inhibitors of these enzymes, in order to recognize and hit hypoxic cells. The cellular uptake, cytostatic activity and capacity to impart an optical sensitization of these particles is shown to display a strong dependence on environmental oxygenation.
Mesoporous Silica Coated Single‐Walled Carbon Nanotubes as a Multifunctional Light‐Responsive Platform for Cancer Combination Therapy
Authors: Liu Jingjing , Wang Chao , Wang Xiaojing , Wang Xin , Cheng Liang , Li Yonggang , Liu Zhuang
Published: November 2014

The development of cancer combination therapies, many of which rely on nanoscale theranostic agents, has received increasing attention in recent years. In this work, polyethylene glycol (PEG) modified mesoporous silica (MS) coated single‐walled carbon nanotubes (SWNTs) are fabricated and utilized as a multifunctional platform for imaging guided combination therapy of cancer. A model chemotherapy drug, doxorubicin (DOX), could be loaded into the mesoporous structure of the obtained SWNT@MS‐PEG nano‐carriers with high efficiency. Upon stimulation under near‐infrared (NIR) light, photothermally triggered drug release from DOX loaded SWNT@MS‐PEG is observed inside cells, resulting in a synergistic cancer cell killing effect. As revealed by both photoacoustic (PA) and magnetic resonance (MR) imaging, we further uncover efficient tumor accumulation of SWNT@MS‐PEG/DOX after intravenous injection into mice. In vivo combination therapy using this agent is further demonstrated in a mouse tumor model, achieving a remarkable synergistic anti‐tumor effect superior to that obtained by mono‐therapy. Our work presents a new type of theranostic nano‐platform, which could load therapeutic molecules with high efficiency, be responsive to external NIR stimulation, and at the same time serve as a diagnostic imaging agent.
Enzyme‐Responsive Release of Doxorubicin from Monodisperse Dipeptide‐Based Nanocarriers for Highly Efficient Cancer Treatment In Vitro
Authors: Zhang He , Fei Jinbo , Yan Xuehai , Wang Anhe , Li Junbai
Published: November 2014

Small aldehyde molecule are demonstrated to induce cationic diphenylalanine to assemble into monodisperse enzyme‐responsive nanocarriers with high biocompatibility and excellent biodegradability. The formation of Schiff base covalent bond and accompanying π–π interaction of aromatic rings are found to be the mainly driving forces for the assembly of the nanocarriers. Interestingly, the nanocarriers show autofluorescence due to the n–π* transitions of C = N bonds, which lends them visually traceable property in living cells. Importantly, the nanocarriers can be taken in by cells and biodegraded in the cells. In addition, doxorubicin is easily loaded into the nanocarriers with high encapsulation amount, and its release can be triggered by tyrisin under physiological conditions. Noticeably, even at a very low drug concentration, the doxorubicin‐loaded nanocarriers still exhibit a much higher killing capacity of HeLa cells in vitro, compared to the equivalent‐dose free doxorubicin, indicating they have a great potential biomedical application.
FeO0.7F1.3/C Nanocomposite as a High‐Capacity Cathode Material for Sodium‐Ion Batteries
Authors: Zhou Yong‐Ning , Sina Mahsa , Pereira Nathalie , Yu Xiqian , Amatucci Glenn G. , Yang Xiao‐Qing , Cosandey Frederic , Nam Kyung‐Wan
Published: November 2014

Searching high capacity cathode materials is one of the most important fields of the research and development of sodium‐ion batteries (SIBs). Here, we report a FeO0.7F1.3/C nanocomposite synthesized via a solution process as a new cathode material for SIBs. This material exhibits a high initial discharge capacity of 496 mAh g−1 in a sodium cell at 50 °C. From the 3rd to 50th cycle, the capacity fading is only 0.14% per cycle (from 388 mAh g−1 at 3rd the cycle to 360 mAh g−1 at the 50th cycle), demonstrating superior cyclability. A high energy density of 650 Wh kg−1 is obtained at the material level. The reaction mechanism studies of FeO0.7F1.3/C with sodium show a hybridized mechanism of both intercalation and conversion reaction.
Acylation of Pyrroles and their Free (N‐H)‐Derivatives via Palladium‐Catalyzed Carbopalladation of Nitriles
Authors: Jafarpour Farnaz , Hazrati Hamideh , Darvishmolla Masoumeh
Published: November 2014

An efficient regioselective synthesis of 2‐acylpyrroles via palladium‐catalyzed addition of pyrroles with benzonitriles and subsequent hydrolysis is developed. The direct acylation reaction of protected as well as (NH)‐free pyrroles proceeded smoothly to afford 2‐acylpyrrole scaffolds of high biological interest.

magnified image
N‐Bromosuccinimide‐Mediated Radical Cyclization of 3‐Arylallyl Azides: Synthesis of 3‐Substituted Quinolines
Authors: Wang Wei‐Xia , Zhang Qing‐Zhao , Zhang Tian‐Qi , Li Zhan‐Shan , Zhang Wei , Yu Wei
Published: November 2014

Visible light irradiation of N‐bromosuccinimide serves as an effective means to convert methyl 2‐(azidomethyl)‐3‐arylpropenoates and 2‐(azidomethyl)‐3‐arylacrylonitriles to the corresponding iminyl radicals via α‐hydrogen abstraction and subsequent extrusion of dinitrogen. Thus formed iminyl radicals then undergo intramolecular ortho attack on the aryl ring, affording methyl quinoline‐3‐carboxylates and quinoline‐3‐carbonitriles respectively.

magnified image
Catalytic syn‐Selective Direct Aldol Reactions of Benzophenone Glycine Imine with Aromatic, Heteroaromatic and Aliphatic Aldehydes
Authors: Lou Sha , Ramirez Antonio , Conlon David A.
Published: November 2014

We have developed highly diastereoselective silver‐catalyzed direct aldol reactions of benzophenone glycine imines with aromatic, heteroaromatic and aliphatic aldehydes. Protection of the secondary alcohol in the aldol product in situ with di‐tert‐butyl dicarbonate was applied to effectively circumvent the retro‐aldol process resulting in improved yields of the aldol products. Only a catalytic amount of base, lithium tert‐butoxide, is required since tert‐butoxide is regenerated during the Boc protection. Computational studies support a stereochemical model in which the axially‐oriented nitrogen atom of the imino (Z)‐enolates coordinates the silver center in a boat conformation. The highly‐ordered transition states favor the formation of the syn aldol products due to the destabilizing interaction between the 1,3‐pseudoaxial alkoxyl group and the aldehyde substituent in the anti isomer.

magnified image
2D and Trap‐Assisted 2D Langevin Recombination in Polymer:Fullerene Blends
Authors: Nyman Mathias , Sandberg Oskar J. , Österbacka Ronald
Published: November 2014

The impact of trapping on the recombination dynamics in polymer:fullerene blends is clarified using the highly ordered bulk heterojunction (BHJ) blend poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene] (PBTTT) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) at different weight ratios as a model system. The recombination dynamics are determined using both transient charge extraction and steady‐state techniques. The results show that both the decay of photogenerated charge and the light ideality factor at a polymer:fullerene weight ratio of 1:4 are fully consistent with 2D Langevin recombination; in the 1:1 case the recombination is seen to be affected by electron trapping. The theory of 2D Langevin recombination is extended to the case with high trap density in agreement with the observations in the 1:1 case. The recombination capture coefficients are derived both for trap‐assisted and band‐to‐band recombination and it can be seen that anisotropic charge transport reduces the capture coefficients in both cases resulting in a reduced overall recombination.
3D Porous γ‐Fe2O3@C Nanocomposite as High‐Performance Anode Material of Na‐Ion Batteries
Authors: Zhang Ning , Han Xiaopeng , Liu Yongchang , Hu Xiaofei , Zhao Qing , Chen Jun
Published: November 2014

A simple and template‐free method for preparing three‐dimensional (3D) porous γ‐Fe2O3@C nanocomposite is reported using an aerosol spray pyrolysis technology. The nanocomposite contains inner‐connected nanochannels and γ‐Fe2O3 nanoparticles (5 nm) uniformly embedded in a porous carbon matrix. The size of γ‐Fe2O3 nanograins and carbon content can be controlled by the concentration of the precursor solution. The unique structure of the 3D porous γ‐Fe2O3@C nanocomposite offers a synergistic effect to alleviate stress, accommodate large volume change, prevent nanoparticles aggregation, and facilitate the transfer of electrons and electrolyte during prolonged cycling. Consequently, the nanocomposite shows high‐rate capability and long‐term cyclability when applied as an anode material for Na‐ion batteries (SIBs). Due to the simple one‐pot synthesis technique and high electrochemical performance, 3D porous γ‐Fe2O3@C nanocomposites have a great potential as anode materials for rechargeable SIBs.
Synthesis and Characterization of High‐Energy, High‐Power Spinel‐Layered Composite Cathode Materials for Lithium‐Ion Batteries
Authors: Bhaskar Aiswarya , Krueger Steffen , Siozios Vassilios , Li Jie , Nowak Sascha , Winter Martin
Published: November 2014

Spinel‐layered composites, where a high‐voltage spinel is incorporated in a layered lithium‐rich (Li‐rich) cathode material with a nominal composition x{0.6Li2MnO3 · 0.4[LiCo0.333Mn0.333Ni0.333]O2} · (1 – x) Li[Ni0.5Mn1.5]O4 (x = 0, 0.3, 0.5, 0.7, 1) are synthesized via a hydroxide assisted coprecipitation route to generate high‐energy, high‐power cathode materials for Li‐ion batteries. X‐ray diffraction patterns and the cyclic voltammetry investigations confirm the presence of both the parent components in the composites. The electrochemical investigations performed within a wide potential window show an increased structural stability of the spinel component when incorporated into the composite environment. All the composite materials exhibit initial discharge capacities >200 mAh g–1. The compositions with x = 0.5 and 0.7 show excellent cycling stability among the investigated materials. Moreover, the first cycle Coulombic efficiency achieve a dramatic improvement with the incorporation of the spinel component. More notably, the composite materials with increased spinel component exhibit superior rate capability compared with the parent Li‐rich material especially together with the highest capacity retention for x = 0.5 composition, making this as the optimal high‐energy high‐power material. The mechanisms involved in the symbiotic relationship of the spinel and layered Li‐rich components in the above composites are discussed.
Home range overlap as a driver of intelligence in primates
Authors: Grueter Cyril C.
Published: November 2014

Various socioecological factors have been suggested to influence cognitive capacity in primates, including challenges associated with foraging and dealing with the complexities of social life. Alexander [Alexander, 1989]. Evolution of the human psyche. In: Mellars P, Stringer C, editors. The human revolution: Behavioural and biological perspectives on the origins of modern humans. Princeton: Princeton University Press. p 455–513] proposed an integrative model for the evolution of human cognitive abilities and complex sociality that incorporates competition among coalitions of conspecifics (inter‐group conflict) as a major selective pressure. However, one of the premises of this model, i.e., that when confronted with inter‐group conflict selection should favor enhanced cognition, has remained empirically untested. Using a comparative approach on species data, I aimed to test the prediction that primate species (n = 104) that face greater inter‐group conflict have higher cognitive abilities (indexed by endocranial volume). The degree of inter‐group conflict/complexity was approximated via the variable home range overlap among groups. I found a significant relationship between home range overlap and endocranial volume, even after controlling for other predictor variables and covariates such as group size and body mass. I conclude that brain size evolution cannot be attributed exclusively to social factors such as group size, but likely reflects a variety of social and ecological determinants including inter‐group conflict which poses cognitive demands on monitoring both the wider social milieu as well as spatial attributes of the habitat. Am. J. Primatol. 77:418–424, 2015. © 2014 Wiley Periodicals, Inc.
Radiographic evaluation of nasal septal deviation from computed tomography correlates poorly with physical exam findings
Authors: Sedaghat Ahmad R. , Kieff David A. , Bergmark Regan W. , Cunnane Mary E. , Busaba Nicolas Y.
Published: November 2014

Background

Performance of septoplasty is dependent on objective evidence of nasal septal deviation. Although physical examination including anterior rhinoscopy and endoscopic examination is the gold standard for evaluation of septal deviation, third‐party payors’ reviews of septoplasty claims are often made on computed tomography (CT) findings. However, the correlation between radiographic evaluation of septal deviation with physical examination findings is unknown.

Methods

Retrospective, blinded, independent evaluation of septal deviation in 39 consecutive patients from physical examination, including anterior rhinoscopy and endoscopic examination, by an otolaryngologist and radiographic evaluation of sinus CT scan by a neuroradiologist. Four distinct septal locations (nasal valve, cartilaginous, inferior/maxillary crest and osseous septum) were evaluated on a 4‐point scale representing (1) 0% to 25%, (2) >25% to 50%, (3) >50% to 75%, and (4) >75% obstruction. Correlation between physical examination and radiographic evaluations was made by Pearson's correlation and quantitative agreement assessed by Krippendorf's alpha.

Results

Statistically significant correlation was detected between physical examination including nasal endoscopy and radiographic assessment of septal deviation only at the osseous septum (p = 0.007, r = 0.425) with low quantitative agreement (α = 0.290). No significant correlation was detected at the cartilaginous septum (p = 0.286, r = 0.175), inferior septum (p = 0.117, r = 0.255), or nasal valve (p = 0.174, r = 0.222). Quantitative agreement at the nasal valve suggested a bias in CT to underestimate physical exam findings (α = −0.490).

Conclusion

CT is a poor substitute for physical examination, the gold standard, in assessment of septal deviation. Clinical decisions about pursuit of septoplasty or third‐party payors’ decisions to approve septoplasty should not be made on radiographic evidence.
Molecular Rare‐Earth‐Metal Hydrides in Non‐Cyclopentadienyl Environments
Authors: Fegler Waldemar , Venugopal Ajay , Kramer Mathias , Okuda Jun
Published: November 2014

Molecular hydrides of the rare‐earth metals play an important role as homogeneous catalysts and as counterparts of solid‐state interstitial hydrides. Structurally well‐characterized non‐metallocene‐type hydride complexes allow the study of elementary reactions that occur at rare‐earth‐metal centers and of catalytic reactions involving bonds between rare‐earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.
Stereospecific Couplings of Secondary and Tertiary Boronic Esters
Authors: Leonori Daniele , Aggarwal Varinder K.
Published: November 2014

This Minireview highlights advances in the Suzuki–Miyaura cross‐coupling of secondary boron reagents for the creation of CC bonds with control of stereochemistry. It also includes non‐transition‐metal coupling of secondary and tertiary boronic esters to electron‐rich aromatics.
Metal‐Free Carbonylations by Photoredox Catalysis
Authors: Majek Michal , Jacobi von Wangelin Axel
Published: November 2014

The synthesis of benzoates from aryl electrophiles and carbon monoxide is a prime example of a transition‐metal‐catalyzed carbonylation reaction which is widely applied in research and industrial processes. Such reactions proceed in the presence of Pd or Ni catalysts, suitable ligands, and stoichiometric bases. We have developed an alternative procedure that is free of any metal, ligand, and base. The method involves a redox reaction driven by visible light and catalyzed by eosin Y which affords alkyl benzoates from arene diazonium salts, carbon monoxide, and alcohols under mild conditions. Tertiary esters can also be prepared in high yields. DFT calculations and radical trapping experiments support a catalytic photoredox pathway without the requirement for sacrificial redox partners.
Ion‐Selective Formation of a Guanine Quadruplex on DNA Origami Structures
Authors: Olejko Lydia , Cywinski Piotr J. , Bald Ilko
Published: November 2014

DNA origami nanostructures are a versatile tool that can be used to arrange functionalities with high local control to study molecular processes at a single‐molecule level. Here, we demonstrate that DNA origami substrates can be used to suppress the formation of specific guanine (G) quadruplex structures from telomeric DNA. The folding of telomeres into G‐quadruplex structures in the presence of monovalent cations (e.g. Na+ and K+) is currently used for the detection of K+ ions, however, with insufficient selectivity towards Na+. By means of FRET between two suitable dyes attached to the 3′‐ and 5′‐ends of telomeric DNA we demonstrate that the formation of G‐quadruplexes on DNA origami templates in the presence of sodium ions is suppressed due to steric hindrance. Hence, telomeric DNA attached to DNA origami structures represents a highly sensitive and selective detection tool for potassium ions even in the presence of high concentrations of sodium ions.
Resistance of paper mill sludge/wood fiber/high‐density polyethylene composites to water immersion and thermotreatment
Authors: Yang Xiaohui , Wang Weihong , Huang Haibing
Published: November 2014

The disposal of paper mill sludge (PMS) is a difficult environmental problem. Thus, PMS has been used as a substitute for wood fiber (WF) to reinforce high‐density polyethylene (HDPE). In this study, we compared PMS–WF–HDPE composites with composites without PMS after water immersion and thermal treatment. Water immersion and thermal treatment were conducted at 25 and 70°C, respectively. The results show that the composites with PMS absorbed less water but lost more of their original flexural properties after immersion; thereby, their strength was compromised. These reduced mechanical properties could be partially restored after redrying. After the thermotreatment, the composites with added PMS lost their weight and flexural properties, whereas the composites without PMS gained flexural strength. The results show that the thermotreatment improved the impact strength of the composites when no more than one‐third of WF was replaced with PMS. Fourier transform infrared spectroscopy and energy‐dispersive X‐ray energy‐dispersive spectroscopy showed that the wood index of the PMS composite decreased more than the index of the non‐PMS composite, whereas the carbonyl index increased more. However, the PMS composite showed a lower increase in the total oxygen/carbon weight ratio. This study suggested that limited amounts of WF could be substituted with PMS to reinforce HDPE. However, WF–PMS–HDPE composites should not be used in hot, humid environments for long periods. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41655.
Topotecan‐Loaded Mesoporous Silica Nanoparticles for Reversing Multi‐Drug Resistance by Synergetic Chemoradiotherapy
Authors: Shen Bo , Zhao Kuaile , Ma Shulan , Yuan Dexiao , Bai Yang
Published: November 2014

Multi‐drug resistance (MDR) has become a major challenge for the further improvement of chemotherapy. Thus, more effective strategies for further enhancing the treatment against cancer by overcoming MDR are warranted. In this study, by the encapsulation of the radiosensitizing drug TPT into mesoporous silica nanoparticles (MSNs), the combined use of drug‐delivered chemotherapy and high‐energy X‐ray induced radiotherapy could produce synergetic chemoradiotherapeutic effects to kill multi‐drug resistant cells through significant DNA damage, thus leading to an efficient circumvention of MDR. We hope that this synergetic dual‐mode treatment strategy may achieve higher oncolytic efficacy and find use in future clinical anti‐MDR applications.
Communication within, outside department leads to consistency, good service across campuses
Authors: Gomez Cynthia
Published: November 2014

Terry L. McCauley began his career in municipal law enforcement and left to work in private security and risk management. But after becoming an adjunct instructor, he decided that higher education was where he belonged. So after 12 years, he joined Oakland Community College's Department of Public Safety.
Achieve greater career success with strategic planning
Authors: Santovec Mary Lou
Published: November 2014

This feature provides you with the guidance you need to help you sharpen your office management skills.
SUMO‐Mimicking Peptides Inhibiting Protein SUMOylation
Authors: Zhao Bo , Villhauer Eric B. , Bhuripanyo Karan , Kiyokawa Hiroaki , Schindelin Hermann , Yin Jun
Published: November 2014

The ubiquitin‐like protein SUMO is transferred through a core E1–E2 cascade composed of the SUMO‐activating enzyme (SAE) and Ubc9 to modify cellular proteins and transmit important biological signals. SAE primarily recognizes the C‐terminal tail of SUMO and catalyzes ATP condensation with the SUMO C‐terminal carboxylate to activate its transfer through the cascade. Here, we used phage display to show that a broad profile of SUMO C‐terminal sequences could be activated by SAE. Based on this, we developed heptamer peptides that could 1) form thioester conjugates with SAE, 2) be transferred from SAE to Ubc9, and 3) be further transferred to the SUMOylation target protein RanGAP1. As these peptides recapitulate the action of SUMO in protein modification, we refer to them as “SUMO‐mimicking peptides”. We found that, once the peptides were conjugated to SAE and Ubc9, they blocked full‐length SUMO from entering the cascade. These peptides can thus function as mechanism‐based inhibitors of the protein SUMOylation reaction.
The Flatstent versus the conventional umbrella devices in the percutaneous closure of patent foramen ovale
Authors: Aral Mert , Mullen Michael
Published: November 2014

Background

Patent foramen ovale (PFO) has been associated with paradoxical embolism leading to stroke/transient ischemic attack, migraine, and neurological decompression sickness. In search for the optimal device that would achieve effective clinical closure with minimal complications, a better device selection based on PFO anatomy and improvements in device design is needed. The Flatstent is a new device designed to treat the highly prevalent long‐tunnel PFOs from within, minimizing the amount of material left behind in an attempt to reduce device‐related complications. The objective is to compare the safety and efficacy of the novel Flatstent versus the conventional umbrella devices in the transcatheter closure of PFO in a nonrandomized, retrospective, single‐center study.

Methods

Between March 2010 and March 2013, 88 patients underwent PFO closure at The Heart Hospital, London with either the novel Flatstent or one of the four conventionally used umbrella devices (GORE Helex Septal Occluder, Occlutech Figulla Flex, Biostar Septal Occluder, and Amplatzer PFO Occluder) depending on their PFO anatomy. Patients were then evaluated with contrast transthoracic echocardiography (TTE) and/or transoesophageal echocardiography (TOE) at 6 weeks and 1 year after the procedure. The residual shunt and complication rates between the Flatstent and umbrella devices were compared.

Results

The Flatstent was used in 27 patients (30.7%), whereas 61 patients (69.3%) received one of the four umbrella devices. Primary efficacy point of clinical closure defined as grade 0 or grade 1; residual shunt was achieved in 81.3% in the Flatstent cohort and 80.3% in the umbrella device group at 6 weeks follow‐up. At 1 year, the clinical closure rates reached 92.6 and 91.8%. There were two device embolizations, one in each cohort during the immediate postoperative period (<24 hrs), with successful retrieval. One patient in the umbrella device group developed transient atrial fibrillation, which was controlled medically. Event recurrence rate was 0% at 1 year.

Conclusion

No difference was found in closure or complication rates between the Flatstent and the umbrella devices. With appropriate preassessment of the PFO anatomy, the Flatstent works as a safe and effective method of treating the PFO from within the tunnel, especially in those with long‐tunnel PFOs. Longer follow‐up is needed to establish superiority. © 2014 Wiley Periodicals, Inc.
Experimental and Theoretical Approaches to the Influence of the Addition of Pyrene to a Series of Pd and Ni NHC‐Based Complexes: Catalytic Consequences
Authors: Valdés Hugo , Poyatos Macarena , Ujaque Gregori , Peris Eduardo
Published: November 2014

A series of Ni and Pd complexes with three different N‐heterocyclic carbene (NHC)‐based ligands (imidazolylidene, benzimidazolylidene and pyrene–imidazolylidene) has been prepared and fully characterized. The influence of the addition of pyrene to solutions containing these complexes is studied by means of NMR and UV/Vis spectroscopies and by cyclic voltammetry. The addition of pyrene to the pyrene–NHC‐containing Pd and Ni complexes gives rise to the formation of adducts by π–π stacking interactions between pyrene and the pyrene group of the NHC ligand. This interaction causes a modification of the electronic properties of the metal, as demonstrated by cyclic voltammetric studies of the Ni–NHC complexes. Theoretical calculations support this type of π‐interactions, and justify the higher interactions observed with the pyrene–NHC containing complexes. The catalytic activities of the complexes were tested in the Suzuki–Miyaura CC coupling and in the α‐arylation of ketones. The addition of pyrene as an external π‐stacking additive does not affect the activities of the complexes in the Suzuki–Miyaura coupling, but this observation may be justified due to the fact that the process is heterogeneously catalyzed, as indicated by the mercury‐drop test. The addition of pyrene to the catalytic α‐arylation of ketones results in a decrease in the activity of the reactions catalyzed by the pyrene–imidazolylidene palladium complex, whereas the other two catalysts do not modify their activity in the presence of this π‐stacking additive.
Palladium‐Catalyzed α‐Arylation of Arylketones at Low Catalyst Loadings
Authors: Marelli Enrico , Corpet Martin , Davies Sian R. , Nolan Steven P.
Published: November 2014

A general catalytic protocol for the α‐arylation of aryl ketones has been developed. It involves the use of a preformed, bench‐stable Pd–N‐heterocyclic carbene pre‐catalyst bearing IHept as an ancillary ligand, and allows the coupling of various functionalized coupling partners at very low catalyst loading. Careful choice of the solvent/base system was crucial to obtain optimum catalyst performance. The pre‐catalyst was also successfully tested in the synthesis of an industrially relevant compound.
Diazo‐ and Transition‐Metal‐Free CH Insertion: A Direct Synthesis of β‐Lactams
Authors: Gomes Luis F. R. , Veiros Luís F. , Maulide Nuno , Afonso Carlos A. M.
Published: November 2014

Carbene intermediates are very useful species for a range of reactions including CH insertions and cycloadditions. They are most commonly generated by metal‐catalyzed release of nitrogen gas from diazo precursors. Herein, we present a novel CH insertion of simple β‐ketoamide substrates, through reaction with (diacetoxyiodo)benzene (DIB) in the presence of a base. This unprecedented transformation bypasses the use of either diazo precursors or metal catalysts and directly delivers β‐lactam products by an iodonium ylide, in a single step under mild conditions. Mechanistic studies support the intermediacy of a free singlet carbene of unique reactivity and selectivity.
Gold(I)‐Catalyzed 1,4‐ and/or 1,5‐Heteroaryl Migration Reactions through Regiocontrolled Cyclizations
Authors: Wang Chengyu , Xie Xin , Liu Jun , Liu Yuanhong , Li Yuxue
Published: November 2014

Gold(I)‐catalyzed regioselective cycloisomerizations of furan‐ynes have been described. The reaction provides a concise access to stereodefined trisubstituted alkenes by endo cyclization with concomitant 1,5‐migration of the furanyl group in the presence of unactivated 3 Å molecular sieves. In the absence of molecular sieves, indene products are generated by exo cyclization, followed by 1,4‐furanyl migration/cyclization. The scope for 1,5‐migrations can be extended to other heterocycles, such as benzofurans, thiophenes, and pyrroles.
The Crystal Structure of a Homodimeric Pseudomonas Glyoxalase I Enzyme Reveals Asymmetric Metallation Commensurate with Half‐of‐Sites Activity
Authors: Bythell‐Douglas Rohan , Suttisansanee Uthaiwan , Flematti Gavin R. , Challenor Michael , Lee Mihwa , Panjikar Santosh , Honek John F. , Bond Charles S.
Published: November 2014

The Zn inactive class of glyoxalase I (Glo1) metalloenzymes are typically homodimeric with two metal‐dependent active sites. While the two active sites share identical amino acid composition, this class of enzyme is optimally active with only one metal per homodimer. We have determined the X‐ray crystal structure of GloA2, a Zn inactive Glo1 enzyme from Pseudomonas aeruginosa. The presented structures exhibit an unprecedented metal‐binding arrangement consistent with half‐of‐sites activity: one active site contains a single activating Ni2+ ion, whereas the other contains two inactivating Zn2+ ions. Enzymological experiments prompted by the binuclear Zn2+ site identified a novel catalytic property of GloA2. The enzyme can function as a Zn2+/Co2+‐dependent hydrolase, in addition to its previously determined glyoxalase I activity. The presented findings demonstrate that GloA2 can accommodate two distinct metal‐binding arrangements simultaneously, each of which catalyzes a different reaction.
ChemInform Abstract: A Practical Method for Metal‐Free Radical Trifluoromethylation of Styrenes with NaSO2CF3.
Authors: Luo Hai‐Qing , Zhang Zhi‐Peng , Dong Wen , Luo Xu‐Zhong
Published: November 2014

Other alkenes such as indene, internal and aliphatic alkenes fail to provide the desired products.
ChemInform Abstract: Novel One‐Pot Synthesis of Polysubstituted Isocoumarins from Arynes and Trifluoroacetylated β‐Diketones.
Authors: Okuma Kentaro , Hirano Koki , Tanabe Yukiko , Itoyama Ryoichi , Miura Atsumi , Nagahora Noriyoshi , Shioji Kosei
Published: November 2014

Compound (VIII) is fully demethylated to afford thunberginol A.
ChemInform Abstract: Synthesis of Pyridoacridines Through Anionic Cascade Ring Closure.
Authors: Petersen Ida Nymann , Kristensen Jesper Langgaard
Published: November 2014

A short synthetic strategy for the construction of pentacyclic heterocycles trough anionic cascade ring closure is developed.
ChemInform Abstract: Microwave‐Assisted Synthesis of Substituted Pyrrolo[2,3‐d]pyrimidines.
Authors: Prieur Vanessa , Rubio‐Martinez Jaime , Font‐Bardia Merce , Guillaumet Gerald , Pujol M. Dolors
Published: November 2014

A sequential route for preparation of triarylated pyrrolopyrimidines starting from common dichloropyrimidine (I) is developed.
ChemInform Abstract: Gombaspiroketals A—C, Sesterterpenes from the Sponge Clathria gombawuiensis.
Authors: Woo Jung‐Kyun , Kim Chang‐Kwon , Kim Seong‐Hwan , Kim Heegyu , Oh Dong‐Chan , Oh Ki‐Bong , Shin Jongheon
Published: November 2014

Gombaspiroketals A (Ib), B (II), and C (Ia) are isolated as a new skeletal class of tetracyclic sesterterpenes from the marine title sponge.
ChemInform Abstract: Copper(II) Triflate as a Mild and Efficient Catalyst for Ferrier Glycosylation: Synthesis of 2,3‐Unsaturated O‐Glycosides.
Authors: Srinivas Batthula , Reddy Thurpu Raghavender , Radha Krishna Palakodety , Kashyap Sudhir
Published: November 2014

1‐Azabicyclo[2.2.2]octan‐3‐ol fails to react.
ChemInform Abstract: Recent Progress in the Synthesis of Functionalized β‐Lactams Through Transition‐Metal‐Catalyzed C(sp3)—H Amidation
Authors: Zhang Qi , Chen Kai , Shi Bing‐Feng
Published: November 2014

Review: [15 refs.
Chemical Resistance and Mechanical Stability of Polymer Film Heat Exchangers
Authors: Laaber Dmitrij , Bart Hans‐Jörg
Published: November 2014

Polyimide and polytetrafluoroethylene (PTFE) films were examined as alternative materials in heat exchangers in respect of their mechanical behavior at temperatures of up to 90 °C and in contact with water, toluene and hexane. It was shown that the PTFE films have a sufficient durability and can be successfully used with these organic liquids. Furthermore, a hydrodynamically optimized prototype of a heat exchanger was designed based on CFD studies coupled with FEM analysis considering geometry deformations of the films caused by pressure loss.
Baseflow Recession Analysis for Flood‐Prone Black Sea Watersheds in Turkey
Authors: Aksoy Hafzullah , Wittenberg Hartmut
Published: November 2014

There is a wide consensus among hydrologists that discharge during the flow recession consists mainly of baseflow, i.e., delayed runoff exfiltrating from the shallow groundwater reservoir and of interflow. It is scarcely noticed, however, that also during floods a considerable portion of discharge is baseflow. Therefore, recession and baseflow analyses do not only concern low flow and groundwater recharge questions but also floods. In this study, the nonlinear reservoir theory is used, assuming nonlinear relation between groundwater storage and baseflow discharge in the river and it is applied for baseflow separation and analysis. Case studies are performed for a time series of daily flows from Melen and Solakli watersheds in the flood‐prone Western and Eastern Black Sea regions in Turkey. The case studies revealed the evident seasonal behavior of baseflow. The water balances showed that the groundwater recharge is higher than the baseflow discharge during the wet season when flows in the streams increase. The baseflow discharge became greater than the groundwater recharge during the months with decreasing flow towards the summer season. It can be concluded that groundwater recharge, outflow and evaporation losses depend highly on seasonality and flow magnitude in the Black Sea region in Turkey.
Analysis of stage and clinical/prognostic factors for lung cancer from SEER registries: AJCC staging and collaborative stage data collection system
Authors: Chen Vivien W. , Ruiz Bernardo A. , Hsieh Mei‐Chin , Wu Xiao‐Cheng , Ries Lynn A. G. , Lewis Denise R.
Published: November 2014

BACKGROUND

The American Joint Committee on Cancer (AJCC) 7th edition introduced major changes in the staging of lung cancer, including the tumor (T), node (N), metastasis (M)—TNM—system and new stage/prognostic site‐specific factors (SSFs), collected under the Collaborative Stage Version 2 (CSv2) Data Collection System. The intent was to improve the stage precision that could guide treatment options and ultimately lead to better survival. This report examines stage trends, the change in stage distributions from the AJCC 6th to the 7th edition, and findings of the prognostic SSFs for 2010 lung cancer cases.

METHODS

Data were from the November 2012 submission of 18 Surveillance, Epidemiology, and End Results (SEER) Program population‐based registries. A total of 344,797 cases of lung cancer, diagnosed in 2004‐2010, were analyzed.

RESULTS

The percentages of small tumors and early‐stage lung cancer cases increased from 2004 to 2010. The AJCC 7th edition, implemented for 2010 diagnosis year, subclassified tumor size and reclassified multiple tumor nodules, pleural effusions, and involvement of tumors in the contralateral lung, resulting in a slight decrease in stage IB and stage IIIB and a small increase in stage IIA and stage IV. Overall about 80% of cases remained the same stage group in the AJCC 6th and 7th editions. About 21% of lung cancer patients had separate tumor nodules in the ipsilateral (same) lung, and 23% of the surgically resected patients had visceral pleural invasion, both adverse prognostic factors.

CONCLUSIONS

It is feasible for high‐quality population‐based registries such as the SEER Program to collect more refined staging and prognostic SSFs that allows better categorization of lung cancer patients with different clinical outcomes and to assess their survival. Cancer 2014;120(23 suppl):3781‐92. © 2014 American Cancer Society.
Clinical and prognostic factors for melanoma of the skin using SEER registries: Collaborative stage data collection system, version 1 and version 2
Authors: Kosary Carol L. , Altekruse Sean F. , Ruhl Jennifer , Lee Richard , Dickie Lois
Published: November 2014

BACKGROUND

The objectives of this article are to assess the completeness of the data collected on site‐specific factors (SSFs) as a part of Collaborative Stage (CS) version 2 and the impact of the transition from the American Joint Committee on Cancer's (AJCC) 6th to 7th edition guidelines on stage distribution.

METHODS

Incidence data for melanomas of the skin from 18 Surveillance, Epidemiology, and End Results (SEER) registries (SEER‐18) were analyzed. Percentages of unknown cases for 7 SSFs were examined, along with staging trends from 2004 to 2010 and differences in AJCC 6th and 7th edition stage distributions for 2010 cases.

RESULTS

Fewer than 10% of cases were coded as unknown for SSFs 1 (measured thickness), 2 (ulceration), and 3 (lymph node metastasis). For the remaining SSFs, 36‐81% of cases were coded as unknown. Stage distributions were relatively consistent across time and between the AJCC 6th and 7th editions, with the exception of stage IA and stage INOS (not otherwise specified), for which a shift in cases was observed between the AJCC 6th and 7th edition guidelines fOR 2010 cases.

CONCLUSIONS

A shift of cases out of stage IA and into stage INOS was observed between the AJCC 6th and 7th edition guidelines for 2010 cases. This was attributed to the high number of cases coded as unknown for SSF7 (primary tumor mitotic count/rate). The percentage of cases coded as unknown varied by SSF. Data completeness presents an issue for SSFs introduced in CS version 2. Cancer 2014;120(23 suppl):3807‐14. © 2014 American Cancer Society.
Analysis of stage and clinical/prognostic factors for colon and rectal cancer from SEER registries: AJCC and collaborative stage data collection system
Authors: Chen Vivien W. , Hsieh Mei‐Chin , Charlton Mary E. , Ruiz Bernardo A. , Karlitz Jordan , Altekruse Sean F. , Ries Lynn A. G. , Jessup J. Milburn
Published: November 2014

BACKGROUND

The Collaborative Stage (CS) Data Collection System enables multiple cancer registration programs to document anatomic and molecular pathology features that contribute to the Tumor (T), Node (N), Metastasis (M) — TNM — system of the American Joint Committee on Cancer (AJCC). This article highlights changes in CS for colon and rectal carcinomas as TNM moved from the AJCC 6th to the 7th editions.

METHODS

Data from 18 Surveillance, Epidemiology, and End Results (SEER) population‐based registries were analyzed for the years 2004‐2010, which included 191,361colon and 73,341 rectal carcinomas.

RESULTS

Overall, the incidence of colon and rectal cancers declined, with the greatest decrease in stage 0. The AJCC's 7th edition introduction of changes in the subcategorization of T4, N1, and N2 caused shifting within stage groups in 25,577 colon and 10,150 rectal cancers diagnosed in 2010. Several site‐specific factors (SSFs) introduced in the 7th edition had interesting findings: 1) approximately 10% of colon and rectal cancers had tumor deposits — about 30%‐40% occurred without lymph node metastases, which resulted in 2.5% of colon and 3.3% of rectal cases becoming N1c (stage III A/B) in the AJCC 7th edition; 2) 10% of colon and 12% of rectal cases had circumferential radial margins <1 mm; 3) about 46% of colorectal cases did not have a carcinoembryonic antigen (CEA) testing or documented CEA information; and 4) about 10% of colorectal cases had perineural invasion.

CONCLUSIONS

Adoption of the AJCC 7th edition by the SEER program provides an assessment tool for staging and SSFs on clinical outcomes. This evidence can be used for education and improved treatment for colorectal carcinomas. Cancer 2014;120(23 suppl):3793‐806. © 2014 American Cancer Society.
Outcome of patients with low‐risk and intermediate‐1‐risk myelodysplastic syndrome after hypomethylating agent failure: A report on behalf of the MDS Clinical Research Consortium
Authors: Jabbour Elias J. , Garcia‐Manero Guillermo , Strati Paolo , Mishra Asmita , Al Ali Najla H. , Padron Eric , Lancet Jeffrey , Kadia Tapan , Daver Naval , O'Brien Susan , Steensma David P. , Sekeres Mikkael A. , Gore Steven D. , Dezern Amy , Roboz Gail J. , List Alan F. , Kantarjian Hagop M. , Komrokji Rami S.
Published: November 2014

BACKGROUND

The hypomethylating agents (HMAs) azacitidine and decitabine are most commonly used to treat patients with higher‐risk myelodysplastic syndromes (MDS). To the authors' knowledge, the prognosis of patients with low‐risk and intermediate‐1–risk MDS by the International Prognostic Scoring System (IPSS) after HMA failure has not been explored comprehensively.

METHODS

The clinical characteristics and treatment outcome of 438 patients with low‐risk and intermediate‐1–risk MDS who were treated with HMAs were retrospectively analyzed.

RESULTS

Using the International Working Group response criteria, the overall objective response to HMA was 35% with a median of 6 cycles of HMA administered, and the median response duration was 7 months. Only 7% of patients had disease that transformed into acute myeloid leukemia while receiving therapy. Of the 290 patients who were evaluable at the time of HMA failure, 77% remained in the lower‐risk disease categories. On multivariate analysis, baseline neutropenia, intermediate‐risk and poor‐risk baseline karyotype, and lack of response to HMA were found to be independently associated with a higher risk of disease progression. With a median follow‐up of 16 months, the median transformation‐free survival and overall survival (OS) after HMA failure were 15 months and 17 months, respectively. On multivariate analysis, only The University of Texas MD Anderson Global Scoring System was found to be independently predictive of outcome, with patients with higher‐risk categories having poor transformation‐free survival (hazards ratio [HR], 1.5;P = .003) and OS (HR, 1.8;P = .002). The administration of salvage therapy was independently associated with better OS only (HR, 0.8;P = .01).

CONCLUSIONS

Outcomes of patients with lower‐risk MDS after HMA failure are poor and the treatment of these patients remains an unmet medical need. OS is a reasonable primary endpoint for clinical studies targeting this population.Cancer2015;121:876–882.©2014 American Cancer Society.
A comparative pharmacokinetic and pharmacodynamic study of FSK0808 versus reference filgrastim after repeated subcutaneous administration in healthy Japanese men
Authors: Matsuguma Kyoko , Matsuki Shunji , Sakamoto Kei , Shiramoto Masanari , Nakagawa Misato , Kimura Miyuki , Irie Shin , Kaneko Daiki , Ohnishi Akihiro
Published: November 2014

FSK0808, a biosimilar of filgrastim, is a recombinant human granulocyte colony‐stimulating factor developed by Fuji Pharmaceuticals and Mochida Pharmaceutical Co., Ltd. We conducted a double‐blind, randomized, crossover study in healthy Japanese men, comparing the number of CD34‐positive cells (CD34+ cells) after repeated subcutaneous administration of either FSK0808 or the reference filgrastim (Gran®). As primary endpoints, we compared the maximum number of CD34+ cells (CD34+ Cmax) and the time to reach CD34+ Cmax (CD34+ tmax). As secondary endpoints, we compared the area under the curve for the number of CD34+ cells over time at the 410 hours time point (CD34+ AUC0–410), the parameters used to calculate the pharmacodynamic index of the absolute neutrophil count, and the pharmacokinetic parameters. Regarding the CD34+ Cmax and the CD34+ AUC0–410 values, the 95% confidence interval (CI) of the differences between the mean values for each drug was within the range of log(0.8)–log(1.25). With respect to the differences in the median values between drugs, the ratio against the reference filgrastim median value in the 95% CI was within the range of ± 0.2 for the CD34+ tmax value. From these results, we considered that these drugs display equivalent pharmacodynamic and pharmacokinetic properties.