bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal‐Centered Excited State in the Bond Rupture and Bond Construction Processes
Authors: Li Huifang , Zhang Lisheng , Zheng lvyin , Li Xun , Fan Xiaolin , Zhao Yi 
Published: August 2016

AbstractPhototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, [Ru(L)(tpy)(DMSO)]n+ (where tpy=2,2’:6’,2’’‐terpyridine; DMSO=dimethyl sulfoxide; L=2,2’‐bipyridine (bpy), n=2; N,N,N’,N’‐tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal‐centered ligand field (3MC) state plays an important role in the excited state S→O isomerization of the coordinated DMSO ligand. If the population of 3MCS state is thermally accessible and no 3MCO can be populated from this state, photoisomerization will be turned off because the 3MCS excited state is expected to lead to fast radiationless decay back to the original 1GSS ground state or photodecomposition along the Ru2+−S stretching coordinate. On the contrary, if the population of 3MCS (or 3MCO) state is inaccessible, photoinduced S→O isomerization can proceed adiabatically on the potential energy surface of the metal‐to‐ligand charge transfer excited states (3MLCTS→3MLCTO). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d6 transition‐metal complexes, which is both experimentally and intellectually challenging as a field of study.
Cyclobuteno[60]fullerenes as Efficient n‐Type Organic Semiconductors
Authors: Reboredo Silvia , Girón Rosa M. , Filippone Salvatore , Mikie Tsubasa , Sakurai Tsuneaki , Seki Shu , Martín Nazario 
Published: August 2016

AbstractCyclobuteno[3,4:1,2][60]fullerenes have been prepared in a straightforward manner by a simple reaction between [60]fullerene and readily available allenoates or alkynoates as organic reagents under basic and mild conditions. The chemical structure of the new modified fullerenes has been determined by standard spectroscopic techniques and confirmed by X‐ray diffraction analysis. Some of these new fullerene derivatives exhibit a remarkable intrinsic electron mobility (determined by using flash‐photolysis time‐resolved microwave conductivity (FP‐TRMC) measurements), which surpasses that of the well‐known phenyl‐C61‐butyric acid methyl ester, thus behaving as promising n‐type organic semiconductors.
Atomic and Ionic Radii of Elements 1–96
Authors: Rahm Martin , Hoffmann Roald , Ashcroft N. W. 
Published: August 2016

AbstractAtomic and cationic radii have been calculated for the first 96 elements, together with selected anionic radii. The metric adopted is the average distance from the nucleus where the electron density falls to 0.001 electrons per bohr3, following earlier work by Boyd. Our radii are derived using relativistic all‐electron density functional theory calculations, close to the basis set limit. They offer a systematic quantitative measure of the sizes of non‐interacting atoms, commonly invoked in the rationalization of chemical bonding, structure, and different properties. Remarkably, the atomic radii as defined in this way correlate well with van der Waals radii derived from crystal structures. A rationalization for trends and exceptions in those correlations is provided.
Photo‐induced Carboiodination: A Simple Way to Synthesize Functionalized Dihydrobenzofurans and Indolines
Authors: Yang Xiaobo , Liu Wenbo , Li Lu , Wei Wei , Li Chao‐Jun 
Published: August 2016

AbstractHerein, we report a simple, redox‐neutral and pH‐neutral photo‐induced carboiodination reaction under very mild conditions. This protocol employs readily available and cheap aryl bromides and sodium iodide as the starting materials to synthesize valuable functionalized dihydrobenzofurans and indolines in good to excellent yields with broad functional‐group compatibility. As examples to demonstrate the utility of this protocol, gram‐scale reactions and further transformations of the products were accomplished towards the synthesis of bioactive drug candidates. Most significantly, to the best of our knowledge, this reaction represents the first example of a cascade atom‐radical‐transfer addition involving the cleavage of aromatic C−Br bond.
Catalyst‐Guided C=Het Hydroarylations by Manganese‐Catalyzed Additive‐Free C−H Activation
Authors: Liang Yu‐Feng , Massignan Leonardo , Liu Weiping , Ackermann Lutz 
Published: August 2016

AbstractExpedient hydroarylations of C=Het bonds (Het=heteroatom) were accomplished by user‐friendly organometallic C−H activation in a positional‐selective manner. The broadly applicable C−H functionalization platform enabled the step‐economical transformation of aldehydes, ketones, and imines under additive‐free reaction conditions. In contrast to palladium, rhodium, ruthenium, rhenium, iridium, nickel, and cobalt catalysis, solely manganese(I) complexes outcompeted the innate substrate control, clearly highlighting the unique power of manganese(I) C−H activation catalysis.
Synthesis of Fluorine‐Doped Hydrophilic Carbon Nanoparticles from Hexafluorobenzene by Femtosecond Laser Pulses
Authors: Okamoto Takuya , Mitamura Koji , Hamaguchi Tomoyuki , Matsukawa Kimihiro , Yatsuhashi Tomoyuki 
Published: August 2016

AbstractWe report on the preparation and characterization of fluorine‐doped hydrophilic carbon nanoparticles by the exposure of hexafluorobenzene or a water/hexafluorobenzene bilayer solution to femtosecond laser pulses. Uniform atom distributions are achieved not only on the particle surface but also inside the particles. The semi‐ionic character of C−F bonds and the non‐aggregating feature of the nanoparticles play key roles in the water‐dispersible character of fluorine‐doped carbon nanoparticles. We suggest the following building‐up process of carbon nanoparticles: the fragmentation of hexafluorobenzene initiated by the electrons generated in laser‐induced plasma followed by the reconstruction of a carbon framework of nanoparticles.
Self‐Assembled 1D‐Nanowire Lasers of Perylenediimides
Authors: Yu Zhenyi , Wu Yishi , Zhang Haihua , Wang Xuedong , Chen Jianwei , Yao Jiannian , Fu Hongbing 
Published: August 2016

AbstractThe 1D nanostructures of perylenediimides (PDIs) have been readily obtained owing to strong cofacial π–π stacking interactions, which, however, subsequently render PDIs weakly emissive in the solid state. Therefore, organic solid‐state lasers based on 1D nanostructures of PDIs have not been achieved yet. Herein, we prepared 1D‐nanowires of N,N’‐bis(1‐ethylpropyl)‐2,5,8,11‐tetrakis(o‐methylphenyl)‐perylene‐3,4:9,10‐tetracarboxylic acid diimide (mp‐PDI), which stack into a loosely J‐type arrangement. J‐aggregation leads to a solid‐state photoluminescence (PL) efficiency φ>18 % and the nanowires of mp‐PDI exhibit excellent Fabry–Perot (FP) mode laser action.
Electron Transport Layer‐Free Solar Cells Based on Perovskite–Fullerene Blend Films with Enhanced Performance and Stability
Authors: Pascual Jorge , Kosta Ivet , Tuyen Ngo T. , Chuvilin Andrey , Cabanero German , Grande Hans J. , Barea Eva M. , Mora‐Seró Iván , Delgado Juan Luis , Tena‐Zaera Ramon 
Published: August 2016

AbstractThe solution processing of pinhole‐free methylammonium lead triiodide perovskite–C70 fullerene (MAPbI3:C70) blend films on fluorine‐doped tin oxide (FTO)‐coated glass substrates is presented. Based on this approach, a simplified and robust protocol for the preparation of efficient electron‐transport layer (ETL)‐free perovskite solar cells is described. Power conversion efficiency (PCE) of 13.6 % under AM 1.5 G simulated sunlight is demonstrated for these devices. Comparative impedance spectroscopy and photostability analysis of the MAPbI3:C70 and single MAPbI3 films compared with conventional compact TiO2 ETL‐based devices are shown. The beneficial impact of using MAPbI3:C70 blend films is emphasized.
Extending the Lifetime of Perovskite Solar Cells using a Perfluorinated Dopant
Authors: Salado Manuel , Ramos F. Javier , Manzanares Valentin M. , Gao Peng , Nazeeruddin Mohammad Khaja , Dyson Paul J. , Ahmad Shahzada 
Published: August 2016

AbstractThe principle limitation of perovskite solar cells is related to their instability and, hence, their limited lifetime. Herein, we employ an imidazolium iodide dopant, 1‐methyl‐3‐(1H,1H,2H,2H‐nonafluorohexyl)‐imidazolium iodide, containing a perfluorous appendage, which leads to prolonged (unencapsulated, under Ar atmosphere) device activities exceeding 100 days without compromising the power conversion efficiency and other photovoltaic parameters. The extended lifetime of the device can be attributed, at least in part, to the hydrophobic nature of the imidazolium iodide salt. The functionalization of the perovskite material was found to have negligible influence on the perovskite crystal structure.
Effect of acute stressor on reproductive behavior differs between urban and rural birds
Authors: Abolins‐Abols Mikus , Hope Sydney F. , Ketterson Ellen D. 
Published: August 2016

AbstractThe life‐history trade‐off between self‐maintenance and reproduction posits that investment in one function decreases investment in the other. Manipulating the costs and benefits of functions involved in a trade‐off may alter this interaction. Here we ask whether investment in self‐maintenance during a stress response alters territorial behavior in wild Dark‐eyed Juncos and whether rural and urban birds, which are known to differ in the magnitude of the stress response (greater in rural), also differ in the degree to which stress reduces territorial behavior. In rural and urban habitats, we measured territorial behavior using song playback, followed by either an acute stressor (capture and collection of a blood sample) or a nonstressful control situation. The following day, we again measured territorial behavior, predicting greater reduction in territorial behavior in individuals exposed to the stressor but a lesser reduction in territorial behavior in the urban as compared to the rural environment. We further assessed individual and population differences in response to stressors by measuring flight initiation distance, breath rate, and corticosterone levels in the blood. The rural population had a higher physiological and behavioral stress response than the urban population, and acute capture stress had a lasting (24 h) negative effect on territorial behavior, but only in the rural habitat. However, individual‐level differences in measures of the stress response did not explain variation in the impact of stress on territorial behavior. Our findings show that stressors can have a negative effect on territorial behavior, but that this effect may differ between populations that vary in their stress ecology.
Fatty acid composition in the fillets of rainbow trout grown in different conditions
Authors: Krstić Milena P. , Mitrović Radmila R. , Marković Radmila V. , Ivanović Jelena S. , Ćirković Miroslav A. , Djordjević Vesna Ž. , Baltić Milan Ž. 
Published: August 2016

The aim of this study was to determine the influence of different feed composition and cultivation on the composition of fatty acids, their relationships, and the cholesterol content in the tissue of rainbow trout (Oncorhynchus mykiss). Trout were reared in ponds at two different altitudes and raised on different feeds. The total amount of monounsaturated fatty acids in fillets of both groups showed no statistically significant difference. However, higher levels of n‐6 fatty acids were found in Pond I trout fillets than in Pond II fillets, while Pond II fillets contained almost even amounts of n‐3 and n‐6 fatty acids. Total cholesterol content in Pond I trout fillets was significantly lower (p < 0.05) than in Pond II fillets. The results indicate that the final composition of the trout fillets was mostly dependent on the feed the live fish had consumed; the altitude of the ponds had less effect. Also, both groups of trout could be used in the human diet as biologically valuable foods.Practical application: Our results show influence of altitude, feed, and fatty acid composition of feed on trout fillets. The average fatty acid level in the trout fillets increased in the order SFA <MUFA <PUFA. Trout fillets contain low levels of cholesterol but high levels of EPA, DPA, and DHA. These facts are important for fish industries and aquaculture producers to design a healthy food.The trout, although grown at two different altitudes, showed differences in their basic chemical composition and in their fatty acid composition which more tended to be related to the composition of their feed. Low cholesterol levels and high levels of EPA, DPA, and DHA, as well as reasonably favorable ratios of n‐3 and n‐6 fatty acids indicate that the trout from both groups could be suitable for use in the human diet as biologically valuable foods.
Low Temperature Complete Combustion of Lean Methane over Cobalt–Nickel Mixed‐Oxide Catalysts
Authors: Shao Chunyu , Li Wenzhi , Lin Qizhao , Huang Qifu , Pi Dong 
Published: August 2016

AbstractCobalt–nickel mixed oxides with different Co/Ni molar ratios were prepared by co‐precipitation and used for the catalytic combustion of lean methane. The catalytic performances for methane combustion were evaluated at steady‐state conditions at temperatures ranging from 250 to 500 °C, which were increased in step sizes of 25 °C. Among the catalysts, the cobalt–nickel mixed‐oxide catalysts with an appropriate Co/Ni ratio exhibit a high catalytic performance for the lean methane combustion, with the catalyst having a Co/Ni molar ratio of 1:4 showing the highest catalytic activity (methane conversion reached 100 % at 425 °C). On the basis of TEM and XRD results, the nanoparticles of the catalysts have a suitable interparticle spacing and more crystal defects. X‐ray photoelectron spectroscopy (XPS) results reveal a high number of surface‐active oxygen species and appropriate aliovalent cobalt ion numbers in the catalysts for high catalytic activity. All these effects contribute to the outstanding performance of these catalysts in the combustion of lean methane at low temperatures.
Involvement of IL‐17A‐producing TCR γδ T cells in late protective immunity against pulmonary Mycobacterium tuberculosis infection
Authors: Umemura Masayuki , Okamoto‐Yoshida Yuko , Yahagi Ayano , Touyama Seigo , Nakae Susumu , Iwakura Yoichiro , Matsuzaki Goro 
Published: August 2016

AbstractIntroductionInterleukin (IL)‐17A is a cytokine originally reported to induce neutrophil‐mediated inflammation and anti‐microbial activity. The CD4+ T cells, which produce IL‐17A, have been well characterized as Th17 cells. On the other hand, IL‐17A‐producing TCR γδ+ T cells have been reported to participate in the immune response at an early stage of infection with Listeria monocytogenes and Mycobacterium bovis in mice. However, the involvement of IL‐17A in protective immunity was not clearly demonstrated in the chronic stage of M. tuberculosis‐infected mice.MethodsWe analyzed role of IL‐17A in host defense against chronically infected M. tuberculosis using IL‐17A KO mice.ResultsWe found that TCR γδ+ T cells are a primary source of IL‐17A, but that mycobacterial antigen‐specific Th17 cells were hardly detected even at the chronic stage of M. tuberculosis infection. IL‐17A‐deficient mice showed a decreased survival rate, and increased bacterial burden in the lungs after the infection when compared to the wild‐type mice. Furthermore, a histological analysis showed an impaired granuloma formation in the infected lungs of IL‐17A‐deficient mice, which was considered to be due to a decrease of IFN‐γ and TNF at the chronic stage.ConclusionOur data suggest that the IL‐17A‐producing TCR γδ+ T cells, rather than the Th17 cells, in the infected lungs are an indispensable source of protective immunity against M. tuberculosis infection.
Application of high resolution OCT to evaluate irregularity of Bowman's layer in asymmetric keratoconus
Authors: Pahuja Natasha , Shroff Rushad , Pahanpate Pratik , Francis Mathew , Veeboy Leio , Shetty Rohit , Nuijts Rudy M. M. A. , Roy Abhijit Sinha 
Published: August 2016

Irregularity of the Bowman's layer (BL) in keratoconus (KC, sample size (n) = 28) and forme fruste keratoconus (FFKC, n = 18) eyes was evaluated. Subjects underwent high resolution OCT imaging (Bioptigen Inc., USA) and corneal tomography (Pentacam v1.20r41, OCULUS Optikgeräte GmbH, Germany). Anterior edge of the BL was segmented. A Bowman's roughness index (BRI) was defined as the sum of the enclosed areas between segmented edge and a smooth 3rd order polynomial fit to the edge. BRI was compared with corneal aberrations, Keratoconus percentage index (KISA), Cone location magnitude index (CLMI) and Belin–Ambrosio enhanced ectasia display overall deviation index (BAD‐D). Area under the curve (AUC) was determined with logistic regression (LR). Mean BRI (×10–3) was 2.12 mm2, 1.81 mm2 and 1.7 mm2 in normal (n = 26), FFKC and KC eyes, respectively (p < 0.001). BAD‐D (0.79) and BRI (0.74) had the best AUC for FFKC. By combining BAD‐D and BRI, the AUC improved to 0.85 (p = 0.01). For KC eyes, KISA (0.94), CLMI (0.88), BAD‐D (0.96) and aberrations had comparable AUC (p > 0.05). However, LR with BRI and other indices didn't improve the AUC in KC eyes (p > 0.05). BRI was significantly reduced in FFKC and KC eyes. It improved the detection of FFKC but not KC eyes.
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From the Volume‐Filling Effect to the Stress‐Bearing Network: The Reinforcement Mechanisms of Carbon Black Filler in Natural Rubber
Authors: Chen Liang , Song Lixian , Li Jing , Chen Pinzhang , Huang Ningdong , Li Liangbin 
Published: August 2016

Using synchrotron‐radiation X‐rays for nanoscale computed tomography (X‐ray nano‐CT), the structure and corresponding reinforcement effects of carbon black (CB) filler at various amounts in natural rubber (NR) are studied during cyclic loading. All structural parameters of the CB filler, which are extracted from X‐ray images—such as the destruction and reconstruction ratios of the aggregates and the network connectivity, show a transition point with the CB content at around 30 phr (phr = parts by weight per hundred parts of rubber). When the CB content is above the transition point, the effective volume fraction exceeds the percolation threshold, and a stress‐bearing filler network can form; this network can effectively transmit the external stress to the entire sample and abruptly enhance the reinforcement factor. Below the percolation threshold, the CB filler is mainly disconnected aggregates, where its reinforcement of the rubber matrix can be mainly described by the volume‐filling effect. Using the dynamic cluster–cluster aggregation (CCA) model, calculations of the mechanical properties related to the CB content suggest that the network structure plays a major role in the reinforcement of the NR.
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Diffusion‐weighted MRI of breast lesions: a prospective clinical investigation of the quantitative imaging biomarker characteristics of reproducibility, repeatability, and diagnostic accuracy
Authors: Spick Claudio , Bickel Hubert , Pinker Katja , Bernathova Maria , Kapetas Panagiotis , Woitek Ramona , Clauser Paola , Polanec Stephan H. , Rudas Margaretha , Bartsch Rupert , Helbich Thomas H. , Baltzer Pascal A. 
Published: August 2016

Diffusion‐weighted MRI (DWI) provides insights into tissue microstructure by visualization and quantification of water diffusivity.Quantitative evaluation of the apparent diffusion coefficient (ADC) obtained from DWI has been proven helpful for differentiating between malignant and benign breast lesions, for cancer subtyping in breast cancer patients, and for prediction of response to neoadjuvant chemotherapy. However, to further establish DWI of breast lesions it is important to evaluate the quantitative imaging biomarker (QIB) characteristics of reproducibility, repeatability, and diagnostic accuracy.In this intra‐individual prospective clinical study 40 consecutive patients with suspicious findings, scheduled for biopsy, underwent an identical 3T breast MRI protocol of the breast on two consecutive days (>24 h). Mean ADC of target lesions was assessed (two independent readers) in four separate sessions. Reproducibility, repeatability, and diagnostic accuracy between examinations (E1, E2), readers (R1, R2), and measurements (M1, M2) were assessed with intraclass correlation coefficients (ICCs), coefficients of variation (CVs), Bland–Altman plots, and receiver operating characteristic (ROC) analysis with calculation of the area under the ROC curve (AUC). The standard of reference was either histopathology (n = 38) or imaging follow‐up of up to 24 months (n = 2).Eighty breast MRI examinations (median E1–E2, 2 ± 1.7 days, 95% confidence interval (CI) 1–2 days, range 1–11 days) in 40 patients (mean age 56, standard deviation (SD) ±14) were evaluated. In 55 target lesions (mean size 25.2 ± 20.8 (SD) mm, range 6–106 mm), mean ADC values were significantly (P < 0.0001) higher in benign (1.38, 95% CI 1.27–1.49 × 10−3 mm2/s) compared with malignant (0.86, 95% CI 0.81–0.91 × 10−3 mm2/s) lesions. Reproducibility and repeatability showed high agreement for repeated examinations, readers, and measurements (all ICCs >0.9, CVs 3.2–8%), indicating little variation. Bland–Altman plots demonstrated no systematic differences, and diagnostic accuracy was not significantly different in the two repeated examinations (all ROC curves >0.91, P > 0.05).High reproducibility, repeatability, and diagnostic accuracy of DWI provide reliable characteristics for its use as a potential QIB, to further improve breast lesion detection, characterization, and treatment monitoring of breast lesions.
Initial testing (stage 1) of tazemetostat (EPZ‐6438), a novel EZH2 inhibitor, by the Pediatric Preclinical Testing Program
Authors: Kurmasheva Raushan T. , Sammons Melissa , Favours Edward , Wu Jianwrong , Kurmashev Dias , Cosmopoulos Katherine , Keilhack Heike , Klaus Christine R. , Houghton Peter J. , Smith Malcolm A. 
Published: August 2016

AbstractBackgroundTazemetostat (EPZ‐6438) is a selective inhibitor of the histone methyltransferase EZH2 and currently in clinical development for non‐Hodgkin lymphoma and genetically defined tumors.ProceduresTazemetostat was tested against the Pediatric Preclinical Testing Program (PPTP) solid tumor xenografts using a dose of 400 mg/kg administered twice daily by oral gavage for 28 days. H3K27me3:H3 ratios were determined in control and treated tumors.ResultsTazemetostat induced significant differences in event‐free survival (EFS) distribution compared with control in nine of 30 (30%) of the xenografts studied. Significant differences in EFS distribution were observed in five of seven (71%) rhabdoid tumor xenograft lines compared with four of 23 (17%) nonrhabdoid xenograft lines (chi‐square [χ2] test P = 0.006). Tazemetostat induced tumor growth inhibition meeting criteria for intermediate and high EFS treated‐to‐control (T/C) activity in two of 25 (8%) and one of 25 (4%) xenografts, respectively. Intermediate and high activity for the EFS T/C metric was observed exclusively among rhabdoid tumor xenografts (three of five rhabdoid tumor vs 0 of 22 nonrhabdoid tumors (χ² test P < 0.001). One rhabdoid tumor xenograft (G401) showed stable disease. For one rhabdoid tumor (G401), delayed tumor regression to tazemetostat was noted following 1 week of tumor growth. Tazemetostat induced significant reduction of H3K27me3 levels in the majority of tumors compared with controls.ConclusionsTazemetostat demonstrated significant antitumor activity in rhabdoid tumor models but showed no consistent activity against any other histology. Tazemetostat reduced H3K27me3 levels irrespective of tumor response. Further preclinical testing to evaluate tazemetostat in combination with other anticancer agents is warranted.