bluuebunny/crossref_metadata_2025 huggingface dataset:
Tumeurs rétropéritonéales primitives : Profils diagnostique, thérapeutique et anatomopathologique
Authors: Aitsakel Adil , Elsayegh Hachem , Benslimane Lounis , Nouini Yassine
Published: December 2015

Introduction : Les tumeurs rétropéritonéales forment un groupe hétérogène de tumeurs rares (< 1 % de toutes les tumeurs), dont 80 % sont malignes. Leur identification et la connaissance de leur pronostic sont les conditions essentielles à leur prise en charge thérapeutique.

Matériel et méthodologie : Entre janvier 2006 et novembre 2012, nous avons colligé onze tumeurs rétropéritonéales. Les dossiers cliniques des patients ont été analysés d’une façon rétrospective; on a noté les caractéristiques cliniques, histologiques et thérapeutiques ainsi que l’évolution après un suivi moyen de 24 mois.

Résultats : La cohorte comprenait sept femmes et quatre hommes avec un âge moyen de 45 ans. Les signes révélateurs sont représentés par les douleurs (77,8 %) et une masse abdominale (55,6 %). Le diagnostic positif était fait par TDM abdomino-pelvienne. Le traitement était surtout chirurgical, visant l’exérèse complète de la masse tumorale, avec ou sans thérapie adjuvante (radiothérapie, chimiothérapie) selon l’analyse histologique. Les tumeurs mésodermiques sont les plus fréquentes (63,6 % ; n = 5) : deux liposarcomes (18 %), deux lymphomes malins (18 %), un hémangiopéricytome (9 %), uné iomyosarcome (9 %), et un cas de rhabdomyosarcome (9 %). Le taux de tumeurs ectodermiques était de 27,4 % (n = 3) ; il s’agit de deux cas de schwannome (18 %) et un cas de ganglioneuroblastome (9 %). Aucune tumeur vestigiale, contre un cas de tumeur pseudo-inflammatoire (9 %). Une évolution favorable a été obervée chez près de la moitié des patients (40 %); on a noté quatre cas de récidive, trois cas de patients perdus de vue, et un décès.

Conclusion : Dans notre série, les tumeurs mésodermiques malignes restent les plus fréquentes, sans prédominance d’âge et de sexe. Les tumeurs rétropéritonéales gardent un pronostic sombre, étant donné que nos patients sont vus à un stade tardif, et aussi du fait du potentiel malin et récidivant de ces tumeurs.
Local tumour ablation for localized kidney cancer: Practice patterns in Canada
Authors: Trudeau Vincent , Larcher Alessandro , Dell'Oglio Paolo , Boehm Katharina , Bishr Mohamed , Karakiewicz Pierre I
Published: December 2015

Introduction: Local tumor ablation (LTA) is a recommended option for the treatment of localized kidney cancer in nonsurgical candidates. We performed a survey to describe the practice patterns of this procedure in Canada.

Methods: An electronic survey was sent by email to all urologists registered to the Canadian Urological Association (CUA). Urologists were queried about general demographic information, LTA availability at their institution (and reasons of non-availability, if it was the case) as well as the type and context of LTA use. 

Results: Overall, 103 individual responses were obtained (response rate of 19.5%). Of those, 58 (56.3%) had access to LTA at their institution. Urologists who had access to LTA were more likely to work at an academic institution (69 vs. 16%, p<0.001). Among individuals who did not use LTA, the main reasons were the lack of staff, such as radiologists, who can assist and/or perform the procedure (64%); and the lack of expertise with the procedure (62%). Among urologists who had access to LTA, percutaneous radiofrequency and cryoablation were the most commonly used (72% and 21%, respectively). However, urologists were rarely involved in those procedures (12%).

Conclusions: In this national survey, we found that a significant proportion of Canadian urologists did not have access to LTA. We also found that when LTA was performed, urologists were rarely involved in the procedures. Those findings represent significant areas for improvement in the access to LTA. The conclusions of this study are limited by the low response rate.
Combined vitamin D and calcium supplementation in vitamin D inadequate patients with urolithiasis: Impact on hypercalciuria and de novo stone formation
Authors: Hesswani Charles , Noureldin Yasser A , Elkoushy Mohamed A , Andonian Sero
Published: December 2015

ABSTRACT

Introduction: We examined the effect of combined vitamin D and calcium supplementation (VDCS) on urinary calcium excretion and de novo stone formation in vitamin D inadequate (VDI) urolithiasis patients.

Methods: We retrospectively reviewed the data of VDI patients (serum 25-hydroxyvitamin D<75 nmol/L) followed at a tertiary stone centre between September 2009 and December 2014. VDI patients with history of urolithiasis, who were placed on VDCS for abnormal bone mineral density or hyperoxaliuria, were included. Hypercalciuric patients and patients on thiazide diuretics were excluded. Metabolic stone workup and two 24-hour urine collections were performed before and after VDCS.

 Results: In total, we inculded 34 patients, with a mean age of 54.8 years and a mean body mass index of 25.7 kg/m2. After VDCS, there was a significant increase in the mean serum 25-hydroxyvitamin D (52.0 vs. 66.4 nmol/L, p<0.001) and the mean urinary calcium excretion (3.80 vs. 5.64 mmol/d, p<0.001). Eight (23.5%) patients developed de novo hypercalciuria. After a median follow-up of 39 (range: 7-60) months, 50% of hypercalciuric patients developed stones compared with 11.5% of non-hypercalciuric patients (p=0.038).

Conclusion: This study showed a significant effect of combined VDCS on mean urinary calcium excretion, de novo hypercalciuria, and stone development in VDI patients with history of urolithiasis. Therefore, VDI urolithiasis patients receiving VDCS are advised to have monitoring with 24-hour urine collections and imaging studies. Although small, the sample size is good enough to validate the statistical outcomes. Prospective studies are needed to confirm these results.
Simultaneous Determination of Eight Hypotensive Drugs of Various Chemical Groups in Pharmaceutical Preparations by HPLC-DAD
Authors: Stolarczyk Mariusz , Hubicka Urszula , Zuromska-Witek Barbara , Krzek Jan
Published: December 2015

A new sensitive, simple, rapid, and precise HPLC method with diode array detection has been developed for separation and simultaneous determination of hydrochlorothiazide, furosemide, torasemide, losartane, quinapril, valsartan, spironolactone, and canrenone in combined pharmaceutical dosage forms. The chromatographic analysis of the tested drugs was performed on an ACE C18, 100 Å, 250 × 4.6 mm, 5 μm particle size column with 0;0.05M phosphate buffer (pH = 3.00)–acetonitrile–methanol (30 + 20 + 50 v/v/v) mobile phase at a flow rate of 1.0 mL/min. The column was thermostatted at 25°C. UV detection was performed at 230 nm. Analysis time was 10 min. The elaborated method meets the acceptance criteria for specificity, linearity, sensitivity, accuracy, and precision. The proposed method was successfully applied for the determination of the studied drugs in the selected combined dosage forms.
Rapid Quantification of Four Anthocyanins in Red Grape Wine by Hydrophilic Interaction Liquid Chromatography/ Triple Quadrupole Linear Ion Trap Mass Spectrometry
Authors: Sun Yongming , Xia Biqi , Chen Xiangzhun , Duanmu Chuansong , Li Denghao , Han Chao
Published: December 2015

The identification and quantification of four anthocyanins (cyanidin-3-O -glucoside, peonidin- 3-O -glucoside, delphinidin-3-O -glucoside, and malvidin-3-O-glucoside) in red grape wine were carried out by hydrophilic interaction liquid chromatography/triple quadrupole linear ion trap MS (HILIC/QTrap-MS/MS). Samples were diluted directly and separated on a Merck ZIC HILIC column with 20 mM ammonium acetate solution–acetonitrile mobile phase. Quantitative data acquisition was carried out in the multiple reaction monitoring mode. Additional identification and confirmation of target compounds were performed using the enhanced product ion mode of the linear ion trap. The LOQs were in the range 0.05–1.0 ng/mL. The average recoveries were in the range 94.6 to 104.5%. The HILIC/QTrap-MS/MS platform offers the best sensitivity and specificity for characterization and quantitative determination of the four anthocyanins in red grape wines and fulfills the quality criteria for routine laboratory application.
Gene Ontology Tools: A Comparative Study
Authors: Muhammad Shahzad  , Kamran Ahsan  , Adnan Nadeem  , Muhammad Sarim
Published: December 2015

Gene ontology (GO) is a key initiative of bioinformatics to provide uniform description of gene product in different public databases. The GO project has initiated 3 (three) structured and organized controlled vocabularies (i.e. ontology) that describes gene products in term of cellular components, biological processes and functions in an independent of species. This resource saves lots of time and effort in finding information of any particular gene from different databases. Since 1998, many tools have been developed which at one end relieves the researchers to search particulars about gene products but at other end makes difficult to opt most appropriate tool for any certain investigation in gene ontology. Here we present the state-of-the-art web based GO tools currently used for biological ontologies. We adopt comparison methodology in conjunction with visualization capabilities and sources of annotation data. This paper considers three GO tools for the said purpose. In Visualization capabilities; Indented List, Node-link & tree and Zoomable capabilities of selected tools have been analyzed. In the data sources section; currently available sources for data annotation have been discussed. This review will facilitate potential users of the GO tools to select an appropriate tool for their need.
La evaluación de competencias profesionales adquiridas a través de la experiencia y vías no formales de formación
Authors: Madrid García Manuel , Solano Lucas Juan Carlos , Baños Páez Pedro
Published: December 2015

En este artículo hacemos una aproximación a los resultados de una investigación realizada en la Universidad de Murcia sobre los procesos de asesoramiento, evaluación y resultados obtenidos en el Procedimiento de Reconocimiento, Evaluación, Acreditación y Registro de las competencias
profesionales (PREAR) para la primera convocatoria de cualificaciones profesionales en la Región de Murcia (Educación Infantil –E.I.-, Atención sociosanitaria a personas en el domicilio –ASPD- y Atención sociosanitaria a personas dependientes en instituciones sociales –ASPDI-).
La hipótesis de partida, que sirvió de marco de referencia para este estudio, se centra en
la idea de que para los candidatos de este proceso es más determinante, en lo que se refiere a conseguir la acreditación de competencias, la propia experiencia laboral, que la formación no formal alcanzada. Esta investigación se realizó sobre el registro de los 450 candidatos/as que participaron en el PREAR (150 en cada una de las tres cualificaciones convocadas) y a un número representativo del personal habilitado como asesor y/o evaluador que también intervino en este procedimiento. Dicho trabajo hizo uso de las fuentes primarias de datos del Instituto de las
Cualificaciones de la Región de Murcia (ICUAM) sobre candidatos y asesores/evaluadores que habían participado en el procedimiento. También se realizaron distintas entrevistas a informantes clave y se organizaron varios grupos de discusión en torno a participantes en los procesos para dichas cualificaciones profesionales.
Asthma control in adults – unfinished business!
Authors: Lalloo Umesh G
Published: December 2015

Asthma treatment has advanced tremendously in the last 3 decades. Medical science has provided evidence based treatment strategies to control over 90% of persons afflicted with asthma. Evidence of the efficacy of this strategy is manifest significantly by a reduction in asthma mortality globally. South Africa, despite being one of the most resourced country on the African continent still has an unacceptably high mortality (1).
An Emissions-Based User Equilibrium Model and Algorithm for Left-turn Prohibition Planning
Authors: Li Qi , Guo Ren-Yong , Yang Wen-Juan
Published: December 2015

The left-turn of vehicles at intersections has significant impacts on urban traffic congestions and accidents, which have negative effect on vehicle emissions causing air pollution. Many urban traffic networks prohibit direct left-turns for transport planning to keep traffic moving efficiently on major roads. As such, this paper proposes a bi-level mathematical model for left-turn prohibition planning considering both travel times and traffic emissions. The lower-level and upper-level are respectively solved by using the Frank-Wolfe algorithm and an improved genetic algorithm. By numerical examples, this paper shows that the improved algorithm can effectively enhance the speed and accuracy of the calculation, and the traffic congestions and emissions can be alleviated by implementing the left-turn prohibition at some carefully selected intersections.
Spesialisering eller samvirke? Om skulptur og arkitektur i gjenreisnings- og vekstårene etter andre verdenskrig
Authors: Aamold Svein
Published: December 2015

One of the characteristics of modernist art and architecture is the insistence on autonomy. What happens if the two media are combined? Will they activate new artistic values – or will their insistence on individual autonomy lead to a differentiation which negates any true dialogue bearing on their status as works of art? These questions are discussed with references to sculptures by Georg Kolbe, Antoine Pevsner, Barbara Hepworth, Jean Arp, Arnold Haukeland and Ramon Isern; and the architecture of Ludwig Mies van der Rohe, Walter Gropius and Erling Viksjø. Also central to these topics are the public debates between architects, sculptors and architectural historians in Europe and America during the first decades after the Second World War. The issues regarding a possible integration of sculpture and architecture were highly contested during these years of optimism and economic growth. For some, the idea of a union between the two media proved to be an ideal that was perhaps never fully accomplished. Many sculptors, however, wanted to create works intended for public spaces, whether in architectural urban settings or in landscapes. Among the architects, the opinions differed from a refusal to include any works of art as part of their buildings, to those who involved in collaborative projects with artists. Others maintained that a new spatial unity could be achieved based on joint efforts on equal terms between sculptors and architects.
Reindrift, hushold og kjønn: Sør-Troms på 1700-tallet, i historisk kildemateriale
Authors: Storm Dikka
Published: December 2015

Focusing on women’s and men’s participation, this article sheds light on the reindeer herding on the island of Hinnøya and in the southern areas of the county of Troms, Northern Norway, during the 18th and 19th centuries. In this region the Sámi and the Norwegian populations have been living side by side for a long period. In addition to hunting and gathering, the economy of the Sámi population was based on farming, fishing, and reindeer herding. Based on a variety of scant sources, the study focuses on the organization of the household and the concept of household as applied to a reindeer herding population. Who was participating in the reindeer herding and how was it organized? Men’s and women’s roles in the household, their economic contributions and their attachments to specific places and areas, are also studied. Public documents such as assize minutes, tax registers, censuses and court testimonies dating from the 1740s onwards have been analysed with regard to ethnographic and biographical studies. The four mentioned sources allow for different approaches to the analysis of gender perspectives, families, kinship, female and male participation, household organizations, economic activities and land use. By comparing this material with ethnographic studies and travel literature, selected individuals are followed – at least partly – through the different phases of their lifetime. Their roles within the household, their social status and kinship shed light on different conditions of their economic base. It is shown, in a systematic discussion of the sources related to specific regions, that women contributed to and participated in the reindeer herding as a part of a combined economy. However, the sources are insufficient for a full reconstruction of the Sámi households in this geographical area.
De tre altarskåpen i Trondenes kyrkas kor: Proveniens, produktion och utbytesbeteende
Authors: Von Bonsdorff Jan
Published: December 2015

Kommer.
Trapped energetic ion dynamics affected by localized electric field perturbations
Authors: Nishimura Seiya
Published: December 2015

Trapped energetic ion orbits in helical systems are numerically simulated using the Lorentz model. Simulation results of precession drift frequencies of trapped energetic ions are benchmarked by those of analytic solutions. The effects of the electric field perturbation localized at the rational surface on trapped energetic ions are examined, where the perturbation has an arbitrary rotation frequency and an amplitude fixed in time. It is found that the trapped energetic ions resonantly interact with the perturbation, when the rotation frequency of the perturbation is comparable to the precession drift frequencies of trapped energetic ions. The simulation results are suggestive to a mechanism of the energetic-ion-induced interchange mode, which might be associated with the fishbone mode observed in helical systems.
Crustal architecture beneath the Tibet‐Ordos transition zone, NE Tibet, and the implications for plateau expansion
Authors: Guo Xiaoyu , Gao Rui , Wang Haiyan , Li Wenhui , Keller G. R. , Xu Xiao , Li Hongqiang , Encarnacion John
Published: December 2015

Most previous studies of the Tibetan Plateau have focused on the processes of crustal thickening and subsequent outward growth. However, lithospheric structure across the tectonic boundaries of the plateau has not yet been fully imaged, and therefore, how geological structures evolved in association with the lateral expansion of the margins remains unclear. Here together with interpretation of regional aeromagnetic anomalies, we employ a recently acquired 165 km long deep seismic reflection image that crosses the northeastern flank of the Tibetan Plateau. The resulting crustal “architecture” suggests that crustal shortening is a primary driver for plateau uplift of northeastern Tibet and that the Xiaoguan Shan to the east of the Liupan Shan belt marks the easternmost edge of the strata that has been affected by the northeastward growth of the plateau. In addition, decoupled crustal deformation owing to differential structural integrity has been accommodated during the subsequent northeastward growth of the plateau.
Duskside enhancement of equatorial zonal electric field response to convection electric fields during the St. Patrick's Day storm on 17 March 2015
Authors: Tulasi Ram S. , Yokoyama T. , Otsuka Y. , Shiokawa K. , Sripathi S. , Veenadhari B. , Heelis R. , Ajith K. K. , Gowtam V. S. , Gurubaran S. , Supnithi P. , Le Huy M.
Published: December 2015

The equatorial zonal electric field responses to prompt penetration of eastward convection electric fields (PPEF) were compared at closely spaced longitudinal intervals at dusk to premidnight sectors during the intense geomagnetic storm of 17 March 2015. At dusk sector (Indian longitudes), a rapid uplift of equatorial F layer to >550 km and development of intense equatorial plasma bubbles (EPBs) were observed. These EPBs were found to extend up to 27.13°N and 25.98°S magnetic dip latitudes indicating their altitude development to ~1670 km at apex. In contrast, at few degrees east in the premidnight sector (Thailand‐Indonesian longitudes), no significant height rise and/or EPB activity has been observed. The eastward electric field perturbations due to PPEF are greatly dominated at dusk sector despite the existence of background westward ionospheric disturbance dynamo (IDD) fields, whereas they were mostly counter balanced by the IDD fields in the premidnight sector. In situ observations from SWARM‐A and SWARM‐C and Communication/Navigation Outage Forecasting System satellites detected a large plasma density depletion near Indian equatorial region due to large electrodynamic uplift of F layer to higher than satellite altitudes. Further, this large uplift is found to confine to a narrow longitudinal sector centered on sunset terminator. This study brings out the significantly enhanced equatorial zonal electric field in response to PPEF that is uniquely confined to dusk sector. The responsible mechanisms are discussed in terms of unique electrodynamic conditions prevailing at dusk sector in the presence of convection electric fields associated with the onset of a substorm under southward interplanetary magnetic field Bz.
Sensitivity of stream dissolved organic carbon to temperature and discharge: Implications of future climates
Authors: Winterdahl Mattias , Laudon Hjalmar , Lyon Steve W. , Pers Charlotta , Bishop Kevin
Published: December 2015

Dissolved organic carbon (DOC) is a significant constituent in aquatic ecosystems with concentrations in streams influenced by both temperature and water flow pathway dynamics associated with changes in discharge (streamflow). We investigated the sensitivity of DOC concentrations in 12 high‐latitude headwater streams to changes in temperature and discharge using a mathematical model. The implications of differences in sensitivities were explored by using downscaled projections of air temperature and discharge to simulate possible trajectories of DOC concentrations in a changing climate. We found two distinct responses: (i) catchments where stream DOC sensitivity was high to temperature but low to discharge and (ii) catchments where stream DOC sensitivity was low to temperature but high to discharge. Streams with strong seasonal DOC dynamics were more sensitive to temperature changes than nonseasonal systems. In addition, stream DOC sensitivity to discharge was strongly correlated with vertical soil water DOC differences in the near‐stream zone. Simulations of possible future changes in DOC concentrations indicated median increases of about 4–24% compared to current levels when using projections of air temperature and discharge but even larger increases were observed for base flow concentrations (13–42%). Streams with high‐temperature sensitivity showed the largest increases in DOC concentrations. Our results suggest that future climatic changes could bring significant increases in surface water DOC concentrations in boreal and hemiboreal areas but that the response ultimately is dependent on vertical soil solution DOC differences and soil organic carbon distribution.
Summer storms trigger soil N2O efflux episodes in forested catchments
Authors: Enanga E. M. , Creed I. F. , Casson N. J. , Beall F. D.
Published: December 2015

Climate change and climate‐driven feedbacks on catchment hydrology and biogeochemistry have the potential to alter the aquatic versus atmospheric fate of nitrogen (N) in forests. This study investigated the hypothesis that during the forest growth season, topography redistributes water and water‐soluble precursors (i.e., dissolved organic carbon and nitrate) for the formation of gaseous N species. Soil nitrous oxide (N2O) and nitrogen (N2) efflux and soil physical and chemical properties were measured in a temperate forest in Central Ontario, Canada from 2005 to 2010. Hotspots and hot moments of soil N2O and N2 efflux were observed in topographic positions that accumulate precipitation, which likely triggered the formation of redox conditions and in turn intercepted the conversion of nitrate N flowing to the stream by transforming it to N2O and N2. There was a strong relationship between precipitation and N2O efflux (y = 0.44x1.22, r2 = 0.618, p < 0.001 in the inner wetland; y = 1.30x1.16 r2 = 0.72, p < 0.001 in the outer wetland) and significantly different N2:N2O ratios in different areas of the wetland (19.6 in the inner wetland and 10.1 in the outer wetland). Soil N2O + N2 efflux in response to precipitation events accounted for 16.1% of the annual N input. A consequence of the higher frequency of extreme precipitation events predicted under climate change scenarios is the shift from an aquatic to atmospheric fate for N, resulting in a significant forest N efflux. This in turn creates feedbacks for even warmer conditions due to increased effluxes of potent greenhouse gases.
Iodine‐Mediated Copper‐Catalyzed Efficient α‐C(sp2)‐Thiomethylation of α‐Oxoketene Dithioacetals with Dimethyl Sulfoxide in One Pot
Authors: Shukla Gaurav , Srivastava Abhijeet , Nagaraju Anugula , Raghuvanshi Keshav , Singh Maya Shankar
Published: December 2015

The direct α‐Csp2H functionalization and thiomethylation of α‐oxoketene dithioacetals (DTAs) has been accomplished with dimethyl sulfoxide (DMSO) in the presence of iodine and a copper(I) salt for the first time. A prerequisite is the in situ iodination of the α‐Csp2 atom of dithioacetals that could offer other reaction channels. The operationally simple one‐pot protocol includes region‐defined consecutive iodination and sulfenylation of the challenging α‐Csp2H bond of dithioacetals employing cheap and readily available reagents. DMSO here plays a dual role as thiomethyl source and solvent.

magnified image
Recyclable Organocatalyst‐Promoted One‐Pot Asymmetric Synthesis of Spirooxindoles Bearing Multiple Stereogenic Centers
Authors: Huang Xin , Pham Kenny , Yi Wenbin , Zhang Xiaofeng , Clamens Cécilia , Hyatt Jeremy H. , Jasinsk Jerry P. , Tayvah Uriel , Zhang Wei
Published: December 2015

A recyclable fluorous bifunctional Cinchona alkaloid/thiourea‐catalyzed and four‐component Michael/Mannich/cyclization sequence has been developed for the asymmetric synthesis of spirooxindoles containing 2‐piperidinone and tetrahydropyridine rings. This one‐pot reaction process affords the products in good to excellent yields and up to 99% ee and 9:1 dr.

magnified image
Evaluating the geometric measure of multiparticle entanglement
Authors: Buchholz Lars Erik , Moroder Tobias , Gühne Otfried
Published: December 2015

We present an analytical approach to evaluate the geometric measure of multiparticle entanglement for mixed quantum states. Our method allows the computation of this measure for a family of multiparticle states with a certain symmetry and delivers lower bounds on the measure for general states. It works for an arbitrary number of particles, for arbitrary classes of multiparticle entanglement, and can also be used to determine other entanglement measures.
In situ Generation of Reticulate Micropores through Covalent Network/Polymer Nanocomposite Membranes for Reverse‐Selective Separation of Carbon Dioxide
Authors: Jeon Eunkyung , Moon Su‐Young , Bae Jae‐Sung , Park Ji‐Woong
Published: December 2015

We demonstrate the synthesis of a microporous covalent‐network membrane derived from co‐continuous blends of a porogenic urea network and a polyimide (PI). We show that the urea networks in the PI matrix may be thermally rearranged while selectively expelling small molecular fragments, thereby forming a new network bearing reticular microporous molecular pathways. The porous structures enable reverse‐selective gas separation, efficiently blocking carbon dioxide to which most polymeric membranes exhibit selective permeability. The proposed method for fabricating microporous organic membranes with highly tunable porosities using a variety of chemical structures and processing parameters is facile and shows promise for the creation of new membrane‐based molecular‐separation techniques.
Die Eisen‐katalysierte intramolekulare C(sp2)‐H‐Aminierung
Authors: Alt Isabel T. , Plietker Bernd
Published: December 2015

Der nukleophile Fe‐Komplex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) katalysiert die direkte intramolekulare C‐H‐Aminierung von α‐Azidobiarylen oder (Azidoaryl)alkenen zu den entsprechenden Carbazolen und Indolen unter milden Reaktionsbedingungen mit geringen Mengen an Katalysator. Dies und die breite Toleranz für funktionelle Gruppen machen dieses Protokoll zu einer attraktiven Alternative zu den etablierten Edelmetall‐basierenden Verfahren.
Small Cause, Great Impact: Modification of the Guanidine Group in the RGD Motif Controls Integrin Subtype Selectivity
Authors: Kapp Tobias G. , Fottner Maximilian , Maltsev Oleg V. , Kessler Horst
Published: December 2015

Due to its unique role as a hydrogen‐bond donor and its positive charge, the guanidine group is an important pharmacophoric group and often used in synthetic ligands. The chemical modification of the guanidine group is often considered to destroy its function. Herein, we show that the N‐methylation, N‐alkylation, or N‐acylation of the guanidine group can be used to modify the receptor subtype specificity of the integrin ligand cilengitide. Using the αvβ6/α5β1‐biselective ligand c(isoDGRkphg) and the αvβ6‐specific ligand c(FRGDLAFp(NMe)K(Ac) as examples, we show that the binding affinities of the ligands can be fine‐tuned by this method to enhance the selectivity for αvβ6. Furthermore, we describe a new strategy for the functionalization of integrin ligands. By introducing longer N‐alkylguanidine and N‐acylguanidine groups, we are able to simultaneously identify a hitherto unknown anchoring point and enhance the subtype selectivity of the ligand.
Thermosensitive copolymer synthesized by controlled living radical polymerization: Phase behavior of diblock copolymers of poly(N‐isopropyl acrylamide) families
Authors: Rwei Syang‐Peng , Chuang Yo‐Ying , Way Tun‐Fun , Chiang Whe‐Yi
Published: December 2015

In this study, we prepared a series of thermosensitive polymers with low polydispersity index (PDI) values by nitroxide‐mediated controlled radical polymerization (NMRP) with 2,2,6,6‐tetramethyl‐1‐piperdinyloxy nitroxide (TEMPO) as a stable nitroxide‐free radical. Poly(N‐isopropyl acrylamide) (PNIPAAm)‐block‐poly(N‐tert‐butyl acrylamide) (PNTBA) was successfully synthesized, first, through polymerization withN‐isopropyl acrylamide to obtain the reactive polymer PNIPAAm‐TEMPO and, second, through polymerization by the addition ofN‐tert‐butyl acrylamide (NTBA). The added molar fraction of NTBA during the second polymerization was adjusted accordingly to obtain the final polymerization product, a thermosensitive polymer (PNIPAAm‐block‐PNTBA), which had a targeted lower critical solution temperature (LCST). The result shows that the synthesis method used in this study effectively controlled the formation of the polymer to obtain a low PDI. The thermosensitive block copolymer, PNIPAAm‐b‐PNTBA (molar ratio = 9:1), with LCSTs in the range 27.7–39.8°C, was obtained through controlled living radical polymerization with PNIPAAm–TEMPO. Specifically, the 5 wt % aqueous solution of PNIPAAm‐b‐PNTBA (molar ratio = 9:1) had an LCST of 37.4°C; this was close to body temperature, 37°C. The 5 wt % aqueous solution of PNIPAAm‐b‐PNTBA (molar ratio = 9:1) showed potential for use in biomedical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43224.
Synthesis and characterization of a novel fluorene‐alt‐carbazole polymer to host green, blue, and red phosphorescence
Authors: Zhao Qinghua , Bai Yu , Fan Zhuxin , Wang Peipei , Li Jinjin , Li Dongxu , Zhang Xinwen
Published: December 2015

A novel fluorene‐alt‐carbazole polymer host Poly(9,9‐dioctyl‐9H‐fluorene‐2,7‐diyl‐alt‐N‐tetrahydropyran‐3,6‐carbazole) (PFCz), composed of N‐tetrahydropyran‐3,6‐carbazole and 9,9‐dioctyl‐2,7‐fluorene in the polymer backbone, was synthesized by Suzuki coupling. The PFCz possesses good thermal stability and proper lowest unoccupied molecular orbital (LUMO)/highest occupied molecular orbital (HOMO) energy levels to facilitate the injection and transport of electrons and holes. Upon doping with blue, green, and red phosphors, red ‐ green ‐ blue (R‐G‐B) phosphorescent devices hosted by PFCz have been fabricated and investigated. In contrast to those of blue and green devices, the red devices give better performances with a maximum luminous efficiency of 4.88 cd/A and a maximum power efficiency of 1.85% at 149.84 cd/m2, due to favorable triplet energy level (ET) of PFCz for red phosphor, bis(2‐methyldibenzo[f,h]quinoxaline)(acetylacetonate)iridium(III) [Ir(MDQ)2(acac)]. Additionally, with different doped concentrations of Ir(MDQ)2(acac), the PFCz‐related red devices emit nearly pure red light with Commission Internationale de L'Eclairage (CIE) coordinates of (0.57, 0.38), (0.60, 0.38), (0.61, 0.38), and (0.62, 0.38), which were very close to the standard red (0.66, 0.34) by the National Television System Committee. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43234.
Doubly robust multiple imputation using kernel‐based techniques
Authors: Hsu Chiu‐Hsieh , He Yulei , Li Yisheng , Long Qi , Friese Randall
Published: December 2015

We consider the problem of estimating the marginal mean of an incompletely observed variable and develop a multiple imputation approach. Using fully observed predictors, we first establish two working models: one predicts the missing outcome variable, and the other predicts the probability of missingness. The predictive scores from the two models are used to measure the similarity between the incomplete and observed cases. Based on the predictive scores, we construct a set of kernel weights for the observed cases, with higher weights indicating more similarity. Missing data are imputed by sampling from the observed cases with probability proportional to their kernel weights. The proposed approach can produce reasonable estimates for the marginal mean and has a double robustness property, provided that one of the two working models is correctly specified. It also shows some robustness against misspecification of both models. We demonstrate these patterns in a simulation study. In a real‐data example, we analyze the total helicopter response time from injury in the Arizona emergency medical service data.
Systematic review of axillary reverse mapping in breast cancer
Authors: Ahmed M , Rubio I T , Kovacs T , Klimberg V S , Douek M
Published: December 2015

Background

Axillary reverse mapping (ARM) assesses the lymphatic drainage of the arm simultaneously with that of the breast, enabling preservation of arm lymphatics during axillary surgery for breast cancer. This article systematically reviews the evidence on the lymphoedema rate and oncological safety of the ARM technique.

Methods

PubMed, Embase and the Cochrane Library were searched systematically for studies that addressed the use of ARM during axillary surgery in breast cancer. Studies were eligible if they performed ARM during sentinel node biopsy (SNB) or axillary node clearance (ANC) for breast cancer in prospective studies of more than 50 patients, with assessment of lymphoedema and oncological outcomes during a minimum follow-up of 6 months.

Results

Eight studies reported data on ARM in 1142 patients undergoing axillary surgery for breast cancer. Lymphoedema rates ranged from 0 to 6 per cent during ARM-assisted SNB, and from 5·9 to 24 per cent during ARM lymphatic preservation at ANC. Crossover nodes between the arm and breast lymphatics were identified in 0–10 per cent of patients, and metastases were present in 0–20 per cent of these patients. ARM nodes were not preserved in between 11 and 18 per cent of patients with ARM nodes identified, and metastases were detected in 0–19 per cent of these patients.

Conclusion

ARM can achieve low rates of lymphoedema, but the risk of metastasis in crossover and clinically suspicious ARM nodes, or those in close proximity to an involved sentinel node, warrants their excision.
Quantitative determination of periplocymarin in rat plasma and tissue by LC‐MS/MS: application to pharmacokinetic and tissue distribution study
Authors: Yan Kaijing , Wang Xiangyang , Jia Yumeng , Chu Yang , Guan Xiufeng , Ma Xiaohui , Li Wei , Pan Guixiang , Zhou Shuiping , Sun He , Liu Changxiao
Published: December 2015

A simple, rapid and sensitive liquid chromatography with tandem mass spectrometry (LC‐MS/MS) method for the determination of periplocymarin in biological samples was developed and successfully applied to the pharmacokinetic and tissue distribution study of periplocymarin after oral administration of periplocin. Biological samples were processed with ethyl acetate by liquid–liquid extraction, and diazepam was used as the internal standard. Periplocymarin was analyzed on a C18 column with isocratic eluted mobile phase composed of methanol and water (containing 0.1% formic acid) at a flow rate of 0.2 mL/min (73:27, v/v). Detection was performed on a triple‐quadrupole tandem mass spectrometer using positive‐ion mode electrospray ionization in the selected reaction monitoring mode. The MS/MS ion transitions monitored were m/z 535.3→355.1 and 285.1→193.0 for periplocymarin and diazepam, respectively. Good linearity was observed over the concentration ranges. The lower limit of quantification was 0.5 ng/mL in plasma and tested tissues. The intra‐and inter‐day precisions (relative standard deviation) were <10.2 and 10.5%, respectively, and accuracies (relative error) were between −6.8 and 8.9%. Recoveries in plasma and tissue were >90%. The validated method was successfully applied to the pharmacokinetic and tissue distribution studies of periplocymarin in rats. Copyright © 2016 John Wiley & Sons, Ltd.
Integration of the free software GenOpt for a thermal engineering course
Authors: Cacabelos Anton , Arce María Elena , Míguez José Luís , Míguez Carla
Published: December 2015

Information and communications technologies (ICT) are being used in engineering fields due to multiple advantages that motivate their introduction in university teaching. A course on thermal engineering has been taught for the past 3 years as part of the industrial engineering degree at the University of Vigo. Energy savings and efficiency are common issues. In a practical classroom, one example is the energy simulations of buildings. These tools can be used to simplify the realization of control strategies for different building HVAC systems, which, in most cases, results in an important reduction in the building's energy consumption over its lifetime. In this paper, the feasibility of using the free software GenOpt for simulation practice and as a tool for teaching and learning inside and outside the classroom is analyzed. These results, together with an analysis of the study plan of the industrial engineering degree at the University of Vigo, allow for the development of new teaching and learning methodologies as well as their implementation in energy simulation practice. © 2015 Wiley Periodicals, Inc. Comput Appl Eng Educ 24:356–364, 2016; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21713
Charge‐Compensated Metallacarborane Building Blocks for Conjugation with Peptides
Authors: Frank René , Ahrens Verena M. , Boehnke Solveig , Beck‐Sickinger Annette G. , Hey‐Hawkins Evamarie
Published: December 2015

The cobalt bis(dicarbollide) complex [commo‐3,3′‐Co(1,2‐C2B9H11)2]− has captured much attention in biochemical and medical contexts, in particular for the treatment of tumors by boron neutron capture therapy (BNCT). Derivatives of cobalt bis(dicarbollide) are commonly prepared through ring‐opening reactions of cyclic oxonium ions, so the corresponding products are usually charged. Furthermore, attempts to incorporate cobalt bis(dicarbollide) into peptides are rare, despite obvious potential advantages. Here the synthesis of an imidazolium‐based charge‐compensated cobalt bis(dicarbollide) building block, which allows additional modifications with moieties of biochemical relevance, such as monosaccharides, is reported. Furthermore, conjugates of these building blocks with the Y1‐receptor‐selective derivative of neuropeptide Y ([F7,P34]‐NPY) retained excellent response to hY1 receptors found to be overexpressed in breast tumors and metastases.
Reprogramming the Biosynthesis of Cyclodepsipeptide Synthetases to Obtain New Enniatins and Beauvericins
Authors: Zobel Sophia , Boecker Simon , Kulke Daniel , Heimbach Dirk , Meyer Vera , Süssmuth Roderich D.
Published: December 2015

Non‐ribosomal peptide synthetases are complex multimodular biosynthetic machines that assemble various important and medically relevant peptide antibiotics. An interesting subgroup comprises the cyclodepsipeptide synthetases from fungi synthesizing cyclohexa‐ and cyclo‐octadepsipeptides with antibacterial, anthelmintic, insecticidal, and anticancer properties; some are marketed drugs. We exploit the modularity of these highly homologous synthetases by fusing the hydroxy‐acid‐activating module of PF1022 synthetase with the amino‐acid‐activating modules of enniatin and beauvericin synthetase, thus yielding novel hybrid synthetases. The artificial synthetases expressed in Escherichia coli and the fungus Aspergillus niger yielded new cyclodepsipeptides, thus paving the way for the exploration of these derivatives for their bioactivity.
Fusion of a Coiled‐Coil Domain Facilitates the High‐Level Production of Catalytically Active Enzyme Inclusion Bodies
Authors: Diener Martin , Kopka Benita , Pohl Martina , Jaeger Karl‐Erich , Krauss Ulrich
Published: December 2015

The increasing number of biocatalytic reactions implemented in chemical synthesis routes raises the urgent need for large amounts of enzymes. Hence, new generic methods are required for their simple and cost‐efficient production. Here, we describe a generally applicable method based on the production of catalytically active inclusion bodies (CatIBs). CatIBs represent a promising new form of biologically produced, carrier‐free, biodegradable enzyme immobilizate. CatIBs are produced in Escherichia coli by expression of a gene fusion consisting of a coiled‐coil domain and a target enzyme. Employing this strategy, the lipase A of Bacillus subtilis (BsLA), the hydroxynitrile lyase of Arabidopsis thaliana (AtHNL), and the 2‐succinyl‐5‐enolpyruvyl‐6‐hydroxy‐3‐cyclohexene‐1‐carboxylate synthase MenD of E. coli (EcMenD) were successfully produced as CatIBs and used in aqueous and micro‐aqueous organic solvent based reaction systems, showing excellent stability and recyclability.
Anion Binding‐Induced White Light Emission using a Water‐Tolerant Fluorescent Molecular Tweezer
Authors: Kumar Rajesh , Srivastava Aasheesh
Published: December 2015

A novel fluorescent molecular tweezer (FMT), built on the pyridine‐2,6‐bis‐carboxamide framework, has been developed that, in presence of a red emitter, gives rise to white light emission in response to the addition of H2PO4− anions. The FMT incorporates two pyrene moieties as fluorescent reporter units and a strategically placed amine residue that imparts pH sensitivity to the fluorescence and offers additional electrostatic/hydrogen‐bonding interactions to the anions. As a result, this FMT selectively binds monoanionic tetrahedral oxyanions such as H2PO4− and HSO4− that contain hydrogen bond donors and acceptors, and can sense their presence in aqueous acetonitrile through changes in fluorescence. Anion binding results in excimer formation by the pyrenes and a bluish‐green emission from the FMT. Both amide and amine residues of the FMT interact with these anions. The binding stoichiometry with H2PO4− and HSO4− was found to be 1:1 and affinity of the FMT for these anions is of the order of 104 m−1. The limit of detection for H2PO4− was found to be 13 nm. Addition of a perylene monoimide‐based red emitter gives rise to panchromatic emission perceived as white light.
Merging Visible‐Light Photocatalysis and Palladium Catalysis for C−H Acylation of Azo‐ and Azoxybenzenes with α‐Keto Acids
Authors: Xu Ning , Li Pinhua , Xie Zuguang , Wang Lei
Published: December 2015

An efficient C−H acylation of azo‐ and azoxybenzenes with α‐keto acids has been developed by a combination of palladium catalysis and visible‐light photoredox catalysis at room temperature under 1.5 W blue LED irradiation. This method tolerates a variety of disubstituted azo‐ and azoxybenzenes, as well as α‐keto acids regardless of the nature of the substituents. A number of aryl ketones were obtained in good yields under mild reaction conditions.
Dioxygen Binding in the Active Site of Histone Demethylase JMJD2A and the Role of the Protein Environment
Authors: Cortopassi Wilian A. , Simion Robert , Honsby Charles E. , França Tanos C. C. , Paton Robert S.
Published: December 2015

Invited for the cover of this issue is the group of Robert S. Paton at the University of Oxford and his collaborators from Brazil and the Czech Republic. The image depicts histone–enzyme complexation and the chemical interactions inside the active site that define the mode of action. Read the full text of the article at 10.1002/chem.201502983.
Thioamination of Alkenes with Hypervalent Iodine Reagents
Authors: Mizar Pushpak , Niebuhr Rebecca , Hutchings Matthew , Farooq Umar , Wirth Thomas
Published: December 2015

An efficient thioamination of alkenes mediated by iodine(III) reagents is described. The use of different sulfur nucleophiles allows the flexible synthesis of 1,2‐aminothiols from alkenes. By employing chiral iodine(III) reagents, a stereoselective version of the thioamination protocol has also been developed.
Ökologische Bewertung ausgewählter Molecular‐Sorting‐Demonstratoren
Authors: Gehring Florian , Lindner Jan Paul , Brandstetter Christian Peter , Albrecht Stefan , Leistner Philip
Published: December 2015

Unter dem Aspekt sich verknappender Ressourcen und der Nachhaltigkeit ist die verstärkte Gewinnung und Nutzung hochwertiger stofflicher Ressourcen aus Abfallströmen erstrebenswert. Eine steigende Individualisierung von Produkten und kürzere Lebenszyklen bringen eine zunehmende Stoffvielfalt bei gleichzeitig sinkenden Stoffmengen mit sich. Im Projekt Molecular Sorting werden beispielhaft Verfahren zur Stofftrennung auf kleinster erforderlicher Ebene entwickelt. Parallel dazu werden Demonstratoren hinsichtlich ihrer Wirkungen auf Umwelt und Ressourcenverfügbarkeit untersucht, was hier anhand zweier Beispiele gezeigt wird. Durch Design for Environment konnten ökologische Aspekte in maßgebende Entwicklungsentscheidungen integriert, Stellschrauben identifiziert und die ökologische Sinnhaftigkeit der neuen Verfahren gezeigt werden.
FMNL2/FMNL3 formins are linked with oncogenic pathways and predict melanoma outcome
Authors: Gardberg Maria , Heuser Vanina D , Koskivuo Ilkka , Koivisto Mari , Carpén Olli
Published: December 2015

While most early (stage I‐II) melanomas are cured by surgery, recurrence is not uncommon. Prognostication by current clinicopathological parameters does not provide sufficient means for identifying patients who are at risk of developing metastases and in need of adjuvant therapy. Actin‐regulating formins may account for invasive properties of cancer cells, including melanoma. Here, we studied formin‐like protein 2 and 3 (FMNL2 and FMNL3) in melanoma by analysing their role in the invasive properties of melanoma cells and by evaluating whether FMNL2 expression is associated with melanoma outcome. Immunohistochemical characterization of FMNL2 in a cohort of 175 primary cutaneous stage I‐II melanomas indicated that high FMNL2 reactivity correlates with poor outcome as evaluated by recurrence free survival (p < 0.0001) or disease specific survival (p < 0.0001). In multivariate analysis, Breslow's thickness (p < 0.05) and FMNL2 expression (p < 0.001) remained as independent prognostic factors. Cellular studies revealed that FMNL2 is a component of filopodia in many melanoma cell lines. Inhibition of either FMNL2 or the closely related FMNL3 affected the maintenance of melanoma cell morphology and reduced migration. Finally, inhibition of the BRAF, PI3K and MAPK oncogenic pathways markedly reduced expression of both FMNL2 and FMNL3 in melanoma cells. The results suggest a major role for FMNL2/FMNL3 formins in melanoma biology and raise the possibility that the novel targeted melanoma drugs may interfere with the cellular properties regulated by these formins.