bluuebunny/crossref_metadata_2025 huggingface dataset:
Diet and weaning age affect the growth and condition of Dover sole (Solea solea L.)
Authors: Rueda-Jasso RA , Conceicão LEC , De Coen W , Francois-Rees J , Sorgeloos P
Published: August 2017

The effect of diet type (frozen Artemia biomass and two inert diets: micro-bound [MB] and micro-extruded [ME]) and two weaning ages (early weaning and late weaning, 50 and 64 days after hatching, respectively) were studied in Solea solea larvae. The experiment lasted 56 and 42 days for early and late weaning, respectively. The mortality results showed the highest values for late weaning (39%) in the Artemia treatment. No significant differences in mortality were observed between the inert diets. The final dry weight values were higher for late weaning than for early weaning. At both weaning ages, fish receiving the same treatments had similar tendencies for dry weight and standard length. Fish fed with MB presented significantly higher dry weight and standard length, followed by ME, while the lowest values at both weaning ages were recorded for the Artemia treatment. Similar amounts of highly unsaturated fatty acid fractions among the inert diets were reflected by the absence of significant differences in the susceptibility to oxidation (thiobarbituric acid reactive substances testing); however, significant differences were found in carbohydrate, protein and lipid contents of whole-body homogenates for both early and late weaning. At the end of the experiment no significant differences in biochemical contents were observed between the two inert diets. The results of this study suggest that weaning starting on day 50 (early weaning), using a good quality inert diet, leads to higher survival, growth and fish condition.
Temporal and spatial variability of phytoplankton pigment concentrations in the Indian Ocean, derived from the CZCS time series images
Authors: Alauddin Talukder ABM
Published: August 2017

A total of 93 monthly global composite remotely sensed ocean color images from the Coastal Zone Color Scanner (CZCS) on board the Nimbus-7 satellite were extracted for the Indian Ocean region (35ºN–55ºS; 30–120ºE) to examine the seasonal variations in phytoplankton pigment concentrations, resulting from large-scale changes in physical oceanographic processes. The CZCS data sets were analyzed with the PC-SEAPAK software, and revealed large phytoplankton blooms in the northwest Arabian Sea and off the Somali coast. The blooms were triggered by wind-driven upwelling during the southwest monsoonal months of August and September. In the northern Arabian Sea, phytoplankton blooms, detected from January to March, appeared to be associated with nutrient enhancement resulting from winter convective mixing. In the Bay of Bengal, higher pigment concentrations were confined to the coastal regions but varied only marginally between seasons both in the coastal and offshore regions. Phytoplankton pigment concentrations were consistently low in the open Indian Ocean. Analysis of pigment concentrations extracted from the monthly-accumulated images revealed that the Arabian Sea sustained a greater biomass of phytoplankton compared with any other region of the Indian Ocean. Overall, the coastal regions of the Indian Ocean are richer in phytoplankton pigment than the open Indian Ocean. The number of images in individual areas was highly variable throughout the region due to varying cloud cover.
Two opposite cases of metal accumulation in ria sediments: Ferrol and Corme-Laxe (Galicia, NW Iberian Peninsula)
Authors: Cobelo-García A , Labandeira A , Prego R
Published: August 2017

The accumulation of heavy metals (Cd, Cu, Pb and Zn) in surface sediments (<63 µm) of the Ferrol and Corme-Laxe rias was studied. These two rias have opposite characteristics from the point of view of both the morphology and the anthropogenic impact. Low metal concentrations were found in the Corme-Laxe Ria, with the highest values observed in the Anllóns River estuary, probably due to a higher lithogenic composition of the sediments. Concentrations in the Corme-Laxe Ria (Cd, 0.10 ± 0.03 µg g–1; Cu, 5 ± 2 µg g–1; Pb, 12 ± 4 µg g–1; and Zn, 49 ± 17 µg g–1) can be used as a good reference for metal background values for sediments from the 18 Galician rias. Although these background values are lower than those previously reported for the Galician coast, they are similar to those found in other uncontaminated coastal and marine systems. The highest concentrations for Ferrol were generally found in the middle part of the ria, which receives the most important urban and industrial impact. The values obtained show evident metal contamination in the middle and inner parts of the Ferrol Ria, with enrichment factors of 4–10 for Cd, 5 for Cu, 2–3 for Pb and 4–5 for Zn.
Age and growth of larval Sardinella aurita (Pisces: Clupeidae) from northeastern Venezuela, determined by otolith microstructure analysis
Authors: Ramírez-M TC , Marín-E BJ
Published: August 2017

Age and growth of Sardinella aurita larvae were analyzed based on daily growth increments in sagitta otoliths. Larvae were obtained from ichthyoplankton samples collected from the outer shelf off Margarita Island and from Mochima Bay (northeastern Venezuela), between March 1999 and January 2001. Total length, standard length (SL) and height of larvae were measured and the otoliths were examined under a light microscope. Larval size ranged from 1.35 to 15.90 mm SL, the Margarita Island larvae being signicantly larger than those from Mochima (t = 18.69; P < 0.001). The three morphological parameters were significantly and positively correlated among themselves and with otolith diameter and age, and fitted to a linear regression model; hence, size growth as a function of age was not different between the localities studied (SL = 2.65 + 1.10 × age; r2 = 0.78, P < 0.001). Growth rates per locality were also determined by backcalculating sizes, with no significant differences (F = 2.60, P > 0.05) between them. The mean backcalculated growth rate was 0.99 mm day–1 and it was not significantly different from the mean growth rate obtained from fitted length-age data (F = 3.32, P > 0.05). Morphological changes in otoliths were evident from the mean daily increment widths, with wider increments in larval otoliths from Margarita Island (H = 42.54, P < 0.001).
As Mudanças na Administração Pública e as Políticas Culturais no Brasil
Authors: Martins Barbara Calçado Lopes , Vitória José Ricardo , Emmendoerfer Magnus Luiz , Fioravante Alexandre Sette Abrantes
Published: August 2017

A trajetória das políticas públicas de cultura demonstra que elas variam bastante de um governo para o outro, e que não houve ainda uma política pública de cultura que fosse considerada em longo prazo, como ocorre em outros setores, como a saúde e a educação. Isso ocorre devido às diferentes compreensões de cultura que cada governo tem. A administração pública também vem passando por várias mudanças, algumas até consideradas “reformas”, devido à grande transformação que apresentam na estrutura do governo. Considerando essas informações, esta pesquisa buscou analisar a influência das mudanças na administração pública brasileira na cultura, através das políticas públicas de cultura. Como resultado observou-se que há uma grande relação entre elas, e as políticas públicas adotadas estão baseadas na compreensão que cada governo tem sobre o significado de cultura.
Formation of Alkanes and Arenes by Reduction
Authors: Larock Richard C. , Zhang Xiaoxia
Published: August 2017

Cyclic Alkanes

Arenes

Alkenes

Alkynes

Organic Halides

Amines and Derivatives

Nitro Compounds

Ethers

Alcohols and Phenols

Sulfur Compounds

Selenium and Tellurium Compounds

Aldehydes and Ketones

Acetals

Carboxylic Acids

Acid Halides

Anhydrides

Esters and Lactones

Nitriles

Isonitriles
Formation of Nitriles, Carboxylic Acids, and Derivatives by Oxidation, Substitution, and Addition
Authors: Larock Richard C. , Yao Tuanli
Published: August 2017

Alkanes

Arenes

Alkenes

Dienes

Alkynes

Alkyl Halides

Amines

Imines and Derivatives

Azides

Nitro Compounds

Nitrothioalkenes

Ethers

Sulfides

Alcohols

Diols

Amino Alcohols

Azido Alcohols

Phenols

Aldehydes and Derivatives

Ketones

Hemiacetals and Lactols

Acetals

Carboxylic Acids

Esters

Amides

Nitriles
Fluoropolymer Nanosheet as a Wrapping Mount for High‐Quality Tissue Imaging
Authors: Zhang Hong , Masuda Ami , Kawakami Ryosuke , Yarinome Kenji , Saito Riku , Nagase Yu , Nemoto Tomomi , Okamura Yosuke
Published: August 2017

In the field of biological microscopy technology, it is still a practical challenge to obtain high‐quality tissue images, due to the tissue desiccation that occurs during observations without an effective sample mounting. Inspired by the use of plastic food wrap, this study proposes the use of polymer thin films (also known as nanosheets) to fix the tissue samples. Water‐repellent nanosheets composed of the amorphous fluoropolymer CYTOP are prepared with adjustable thicknesses and their hydrophobicity, transparency, and adhesion strength are evaluated. They show excellent water‐retention effect and work well for sample fixation. By wrapping cleared mouse brain slices with a 133 nm thick CYTOP nanosheet, this study achieves high spatial resolution neuron images while scanning over a large area for a long period of time. No visible artifacts arising from sample shrinkage can be detected. This study also expects that nanosheet wrapping could be effective over a longer time span by combination with conventional agarose embedding.
Rhodium(III)‐Catalyzed C−H Activation of O‐Acetyl Ketoximes/N‐Methoxybenzamides toward the Synthesis of Isoquinoline/Isoquinolone‐Fused Bicycles
Authors: Vijayan Ajesh , Jumaila Choorappulan Ummu , Radhakrishnan Kokkuvayil Vasu
Published: August 2017

An efficient rhodium(III)‐catalyzed C−H activation approach for the construction of fused heterocyclic motifs with urea‐derived bicyclic olefins has been demonstrated. A rhodium‐catalyzed reaction of O‐acetyl ketoximes with these bicyclic motifs furnished isoquinoline derivatives, whereas isoquinolone‐fused bicyclic olefins were obtained with the reaction of N‐methoxybenzamides.
Traversing Biosynthetic Carbocation Landscapes in the Total Synthesis of Andrastin and Terretonin Meroterpenes
Authors: Xu Gong , Elkin Masha , Tantillo Dean J. , Newhouse Timothy R. , Maimone Thomas J.
Published: August 2017

Meroterpenes derived from dimethylorsellinic acid (DMOA) and farnesyl pyrophosphate have attracted much biosynthetic attention, yet only recently have synthetic solutions to any family members appeared. A key point of divergence in DMOA‐derived meroterpene biosynthesis is the protoaustinoid A carbocation, which can be diverted to either the berkeleyone, andrastin, or terretonin structural classes by cyclase‐controlled rearrangement pathways. Shown herein is that the protoaustinoid bicyclo[3.3.1]nonane nucleus can be reverted to either andrastin or terretonin ring systems under abiotic reaction conditions. The first total syntheses of members of these natural product families are reported as their racemates.
Hydrogels with Reversible Mechanics to Probe Dynamic Cell Microenvironments
Authors: Rosales Adrianne M. , Vega Sebastián L. , DelRio Frank W. , Burdick Jason A. , Anseth Kristi S.
Published: August 2017

The relationship between ECM mechanics and cell behavior is dynamic, as cells remodel and respond to changes in their local environment. Most in vitro substrates are static and supraphysiologically stiff; thus, platforms with dynamic and reversible mechanical changes are needed. Herein, we developed hyaluronic acid‐based substrates capable of sequential photodegradation and photoinitiated crosslinking reactions to soften and then stiffen the hydrogels over a physiologically relevant range of moduli. Reversible mechanical signaling to adhered cells was demonstrated with human mesenchymal stem cells. In situ hydrogel softening (from ca. 14 to 3.5 kPa) led to a decrease in the cell area and nuclear localization of YAP/TAZ, and subsequent stiffening (from ca. 3.5 to 28 kPa) increased the cell area and nuclear localization of YAP/TAZ. Each photoreaction was cytocompatible and tunable, rendering this platform amenable to studies of dynamic mechanics on cell behavior across many cell types and contexts.
Remote meta‐C–H Cyanation of Arenes Enabled by a Pyrimidine‐Based Auxiliary
Authors: Bag Sukdev , Jayarajan Ramasamy , Dutta Uttam , Chowdhury Rajdip , Mondal Rahul , Maiti Debabrata
Published: August 2017

An easily removable pyrimidine‐based auxiliary has been employed for the remote meta‐C−H cyanation of arenes. The scope of this Pd‐catalyzed cyanation reaction using copper(I) cyanide as the cyanating agent was demonstrated with benzylsilanes, benzylsulfonates, benzylphophonates, phenethylsulfonates, and phenethyl ether derivatives. The method was utilized for the synthesis of pharmaceutically valuable precursors.
Rapid Access to Nanographenes and Fused Heteroaromatics by Palladium‐Catalyzed Annulative π‐Extension Reaction of Unfunctionalized Aromatics with Diiodobiaryls
Authors: Matsuoka Wataru , Ito Hideto , Itami Kenichiro
Published: August 2017

Efficient and rapid access to nanographenes and π‐extended fused heteroaromatics is important in materials science. Herein, we report a palladium‐catalyzed efficient one‐step annulative π‐extension (APEX) reaction of polycyclic aromatic hydrocarbons (PAHs) and heteroaromatics, producing various π‐extended aromatics. In the presence of a cationic Pd complex, triflic acid, silver pivalate, and diiodobiaryls, diverse unfunctionalized PAHs and heteroaromatics were directly transformed into larger PAHs, nanographenes, and π‐extended fused heteroaromatics in a single step. In the reactions that afford [5]helicene substructures, simultaneous dehydrogenative ring closures occur at the fjord regions to form unprecedented larger nanographenes. This successive APEX reaction is notable as it stiches five aryl–aryl bonds by C−H functionalization in a single operation. Moreover, the unique molecular structures, crystal‐packing structures, photophysical properties, and frontier molecular orbitals of the thus‐formed nanographenes were elucidated.
High‐Level Spectroscopy, Quantum Chemistry, and Catalysis: Not just a Passing Fad
Authors: Neese Frank
Published: August 2017

Quantum chemistry can be used as a powerful link between theory and experiment for studying reactions in all areas of catalysis. The key feature of this approach is the combination of quantum chemistry with a range of high‐level spectroscopic methods. This allows for conclusions to be reached that neither theory nor experiment would have been able to obtain in isolation.
Metal complexes of chalcone analogue: Synthesis, characterization, DNA binding, molecular docking and antimicrobial evaluation
Authors: Atlam Faten M. , El‐Nahass Marwa N. , Bakr Eman A. , Fayed Tarek A.
Published: August 2017

A novel chalcone, namely 5‐(4‐(dimethylamino)phenyl)‐1‐(thiophen‐2‐yl)penta‐2,4‐dien‐1‐one, DMATP, and its complexes with nickel(II), vanadium(III), palladium(II) and platinum(II) metal ions were synthesized and characterized using a set of chemical and spectroscopic tools including elemental analysis, electrical conductance, magnetic susceptibility and spectral techniques. The interactions of the synthesized chalcone and its metal complexes with DNA were studied using steady‐state absorption and emission techniques as well as viscosity and electrochemical measurements. The obtained results confirm DNA intercalation. Additionally, theoretical studies were performed for all the investigated compounds using DFT/B3LYP calculations. The optimized geometries are found to be in good agreement with the suggested experimental structures. The bond lengths, bond angles, chemical reactivity, energy components, binding energy and dipole moment were evaluated. Also, theoretical infrared intensities and thermodynamic parameters for all compounds were calculated. Molecular docking calculations show that the Ni(II) complex exhibits the highest DNA binding activity, which agrees well with the experimental results. Finally, the compounds were screened for antimicrobial activity using several microorganisms.
Syntheses, silylation, characterization, and antimicrobial and antifertility activities of organoboron derivatives of some bioactive monofunctional bidentate semicarbazones
Authors: Bhomia Jyoti , Sharma Jyoti , Lakhne Rucha , Sharma Rachna , Gupta R.S. , Sharma Ram Avatar , Singh Yashpal
Published: August 2017

Some new mononuclear organoboron derivatives of the type PhBL1–5(OH) (1a–1e) were synthesized by the reaction of PhB(OH)2 and LH (LH = OC(NH2)NH:NC(CH3)4C6H4R, where R = H (L1H); CH3(L2H); OCH3(L3H); Cl (L4H); Br (L5H)) in 1:1 molar ratio in refluxing tetrahydrofuran (THF). This was followed by the reactions of PhBL1–5(OH) with NH(SiMe3)2 in 2:1 molar ratio in THF to yield new heterodinuclear derivatives of the type PhBL1–5(OSiMe3) (2a–2e). All these newly synthesized complexes were characterized using elemental analyses and their probable structure was proposed on the basis of infrared, 1H NMR, 13C NMR, 11B NMR and 29Si NMR spectral data and mass spectrometry. Semicarbazone ligands and their corresponding mono‐ and heterodinuclear boron derivatives were screened against pathogenic bacteria (E. coli and P. aeruginosa) and fungi (A. niger and P. peniculosum) to examine their antimicrobial activities. Representative compounds of each series of mono‐ and heterodinuclear boron derivatives and a ligand were screened for their antifertility activity on male adult Wistar rats.
Enhanced dielectric and ferroelectric properties induced by Ag @ Pb(Zr,Ti)O3 in poly(vinyl alcohol) matrix composites: A solution casting approach
Authors: Moharana Srikanta , Joshi Sourav K. , Mahaling Ram Naresh
Published: August 2017

The present research work focused on the dielectric and electrical properties of silver (Ag) doped Pb(Zr,Ti)O3 (PZT) particles embedded in a matrix of poly(vinyl alcohol) (PVA) via solution casting technique. The structural analysis confirmed the presence of Ag particles and the microstructural study revealed that both Ag and PZT particles were successfully homogenized over the polymer matrix. The Ag–PZT–PVA composites showed enhanced dielectric properties over a wide range of frequency and the dielectric constant value of such composites was significantly increased to 366 (100 Hz) at 1.1 wt % filler loading. The percolation threshold of the Ag–PZT–PVA composites was found to be 0.9 wt %. The experimental result well fitted to the percolation theory. The enhancement of dielectric constant of the resulting composite systems might be attributed to the increment of conductivity of the interlayer between PZT and PVA due to the presence of Ag particles, which improved the space charge polarization and Maxwell–Wagner–Sillars (MWS) polarization effects. Furthermore, the remnant polarization of the unpoled Ag–PZT–PVA composites (2Pr ∼1.48 µC/cm2 for 1.1.wt % of Ag–PZT) has also improved, which is favorable for enhanced ferroelectric properties of the composites. The present findings of the composites might be exploited in the potential application of high performance energy storage devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45583.
Design of modular dual enzyme‐responsive peptides
Authors: Boehnke Natalie , Maynard Heather D.
Published: August 2017

Dual enzyme‐responsive peptides were synthesized by masking the ɛ‐amine of lysine with various enzyme substrates. Enzymatic cleavage of these sequences unmasked the ɛ‐amine, allowing for further digestion by a second enzyme, which was monitored colorimetrically. This modular peptide design should provide substrates for a large combination of clinically relevant enzymes.
Anticancer efficacy of the hypoxia‐activated prodrug evofosfamide is enhanced in combination with proapoptotic receptor agonists against osteosarcoma
Authors: Liapis Vasilios , Zysk Aneta , DeNichilo Mark , Zinonos Irene , Hay Shelley , Panagopoulos Vasilios , Shoubridge Alexandra , Difelice Christopher , Ponomarev Vladimir , Ingman Wendy , Atkins Gerald J. , Findlay David M. , Zannettino Andrew C. W. , Evdokiou Andreas
Published: August 2017

Tumor hypoxia is a major cause of treatment failure for a variety of malignancies. However, hypoxia also leads to treatment opportunities as demonstrated by the development of compounds that target regions of hypoxia within tumors. Evofosfamide is a hypoxia‐activated prodrug that is created by linking the hypoxia‐seeking 2‐nitroimidazole moiety to the cytotoxic bromo‐isophosphoramide mustard (Br‐IPM). When evofosfamide is delivered to hypoxic regions of tumors, the DNA cross‐linking toxin, Br‐IPM, is released leading to cell death. This study assessed the anticancer efficacy of evofosfamide in combination with the Proapoptotic Receptor Agonists (PARAs) dulanermin and drozitumab against human osteosarcoma in vitro and in an intratibial murine model of osteosarcoma. Under hypoxic conditions in vitro, evofosfamide cooperated with dulanermin and drozitumab, resulting in the potentiation of cytotoxicity to osteosarcoma cells. In contrast, under the same conditions, primary human osteoblasts were resistant to treatment. Animals transplanted with osteosarcoma cells directly into their tibiae developed mixed osteosclerotic/osteolytic bone lesions and consequently developed lung metastases 3 weeks post cancer cell transplantation. Tumor burden in the bone was reduced by evofosfamide treatment alone and in combination with drozitumab and prevented osteosarcoma‐induced bone destruction while also reducing the growth of pulmonary metastases. These results suggest that evofosfamide may be an attractive therapeutic agent, with strong anticancer activity alone or in combination with either drozitumab or dulanermin against osteosarcoma.
Characteristics and clinical outcomes of repeat endovascular therapy after infrapopliteal balloon angioplasty in patients with critical limb ischemia
Authors: Kobayashi Norihiro , Hirano Keisuke , Yamawaki Masahiro , Araki Motoharu , Sakai Tsuyoshi , Sakamoto Yasunari , Mori Shinsuke , Tsutsumi Masakazu , Honda Yohsuke , Tokuda Takahiro , Makino Kenji , Shirai Shigemitsu , Ito Yoshiaki
Published: August 2017

Objectives

We clarified characteristics and clinical outcomes of critical limb ischemia (CLI) patients who underwent repeat endovascular therapy (EVT) for infrapopliteal lesions.

Background

High restenosis rate after infrapopliteal EVT remains a major concern.

Methods

Patients with CLI who underwent EVT between April 2007 and February 2014, were divided into the following three groups according to how often EVT was repeated: Group A, no repeat of EVT; Group B, EVT repeated once/twice; and Group C, EVT repeated ≥3 times.

Results

Wound healing rates at 1 year were 93.9% in Group A, 77.1% in Group B, and 27.3% in Group C (P < 0.001). Limb salvage rates at 3 years were 93.0, 88.5, and 57.1%, respectively (P = 0.001). Amputation‐free survival rates at 3 years were 60.8, 51.2, and 29.2%, respectively (P = 0.019). Multivariate analysis revealed that hemodialysis (OR 3.413, 95% CI 1.263–9.225, P = 0.016), low ejection fraction (OR 7.758, 1.049–57.360, P = 0.045), and clinical stage assessed by SVS WIfI (OR 2.440, 1.417–4.203, P = 0.001) were independent predictors of repeat EVT. The rate of requirement for repeat EVT significantly increased as clinical stage became more severe (repeat EVT rate: 0% in CS 1, 28.6% in CS 2, 34.0% in CS 3, and 45.7% in CS 4, P < 0.001).

Conclusions

The clinical outcomes of CLI patients requiring repeat EVT three or more times were poor. The SVS WIfI clinical stage may be useful to predict the necessity of repeat EVT.
Structurally Stable Mesoporous Hierarchical NiMoO4 Hollow Nanofibers for Asymmetric Supercapacitors with Enhanced Capacity and Improved Cycling Stability
Authors: Sudheendra Budhiraju Venkata , Sharma Ashutosh , Sivakumar Sri
Published: August 2017

Herein, we report, for the first time, the facile synthesis of four different mesoporous hierarchical structures of NiMoO4 through electrospinning: solid nanofibers, porous nanofibers, hollow nanofibers, and microplates of NiMoO4. All of these structures were investigated as electrode materials for supercapacitors. Amongst these, hollow NiMoO4 nanofibers demonstrated superior electrochemical performance with a high specific capacity of 214 mAh g−1 (1920 F g−1) at a current density of 2 A g−1 and a capacity retention of 92 % after 3000 cycles. An asymmetric supercapacitor fabricated from a hollow NiMoO4 nanofiber cathode and an activated carbon anode displayed a high specific capacity of 49 mAh g−1 (110 F g−1) at a current density of 1 A g−1 and a capacity retention of 97 % after 5000 cycles. At this current density, the device delivered a high energy density of 39 Wh Kg−1 and a power density of 798 W Kg−1 at a relatively high mass loading of 5 mg cm−2 of active material on the substrate. This impressive performance of hollow NiMoO4 nanofibers could be attributed to their mesoporous surface with high specific surface area (ca. 105 m2 g−1), the hollow core and the interconnectedness of the fibers that improve the electrolyte penetration, increase the rate of the surface redox reactions and allow for faster transport of the charges.
Supramolecular Host–Guest Inclusion for Distinguishing Cucurbit[7]uril‐Based Pseudorotaxanes from Small‐Molecule Ligands in Coordination Assembly with a Uranyl Center
Authors: Mei Lei , Xie Zhen‐Ni , Hu Kong‐qiu , Yuan Li‐Yong , Gao Zeng‐Qiang , Chai Zhi‐Fang , Shi Wei‐Qun
Published: August 2017

Although the capability of supramolecular pseudorotaxane/rotaxane systems as ligands for coordination with actinides has been identified by the on‐going emerging of uranyl–organic polyrotaxane compounds, it is, however, still unknown how supramolecular inclusion affects the coordination assembly of the simple “axle” ligand with uranyl species. Herein, a semi‐rigid organic dicarboxylate compound [BzBPCEt]Br2 (L1) is selected as a small‐molecule “axle” ligand and the corresponding cucurbit[7]uril (CB7)‐based [2]pseudorotaxane ligand, [BzBPCEt]Br2@CB7 (L1@CB7) has been also synthesized through CB7‐based inclusion in this work. A detailed comparison between uranyl complexes from the “axle” ligand L1 and those from pseudorotaxane L1@CB7 has been conducted, demonstrating the significant role of CB7‐based inclusion in distinguishing supramolecular pseudorotaxane ligands from small‐molecule dicarboxylates in uranyl coordination assembly. Notably, the impact of supramolecular inclusion on the “axle” linker in the system with cucurbituril macrocycles involved is established for the first time. Detailed structure decipherment suggests that the significant effect of CB7 is attributed to hydrothermal stabilization of the “axle” ligand or increased steric hindrance to the groups nearby originated from the bulky size of macrocyclic CB7.
Reductive Eliminations from Diarylpalladium(II) Complexes: A Combined Experimental and Computational Investigation
Authors: Gensch Tobias , Thoran Robert , Richter Nils , Knölker Hans‐Joachim
Published: August 2017

The diverse mechanisms for the reductive elimination of biaryl compounds from diarylpalladium(II) complexes with a tetradentate ligand were investigated through a combined experimental and computational study. At least four distinct chemical triggers with specific regioselectivity exist for this elimination. Heating of the complexes in inert solvents (e.g., para‐xylene) reveals their relatively high thermal stability as reflected by a very high barrier for a unimolecular reductive elimination. In contrast, electron‐donor ligands like triphenylphosphine induce a facile reductive elimination via twofold associative ligand exchange as confirmed by kinetic experiments, which are in good agreement with the computational results. Oxidants, such as H2O2, can trigger an oxidation‐induced reductive elimination via palladium(IV) intermediates at room temperature. Rearrangement of the diarylpalladium(II) complexes can occur in organic acids, facilitating a reductive elimination with distinct regiochemical outcome.
(CF3)3Au as a Highly Acidic Organogold(III) Fragment
Authors: Pérez‐Bitrián Alberto , Baya Miguel , Casas José M. , Falvello Larry R. , Martín Antonio , Menjón Babil
Published: August 2017

The Lewis acidity of perfluorinated trimethylgold (CF3)3Au was assessed by theoretical and experimental methods. It was found that the (CF3)3Au unit is much more acidic than its nonfluorinated analogue (CH3)3Au, and probably sets the upper limit of the acidity scale for neutral organogold(III) species R3Au. The significant acidity increase on fluorination is in line with the CF3 group being more electron‐withdrawing than CH3. The solvate (CF3)3Au⋅OEt2 (1) is presented as a convenient synthon of the unsaturated, 14‐electron species (CF3)3Au. Thus, the weakly coordinated ether molecule in 1 is readily replaced by a variety of neutral ligands (L) to afford a wide range of (CF3)3Au⋅L compounds, which were isolated and characterized. Most of these mononuclear compounds exhibit marked thermal stability. This enhanced stabilization can be rationalized in terms of substantially stronger [Au]−L interactions with the (CF3)3Au unit. An affinity scale of this single‐site, highly acidic organogold(III) fragment was calculated by DFT methods and experimentally mapped for various neutral monodentate ligands. The high‐energy profile calculated for the fluorotropic [Au]−CF3⇌F−[Au]←CF2 process makes this potential decomposition path unfavorable and adds to the general stabilization of the fragment.
Study of the effect of the operating parameters on the separation of bioactive compounds of palm oil by ultra‐high performance supercritical fluid chromatography using a design of experiments approach
Authors: de Souza Guedes Luciana , Jardim Isabel Cristina Sales Fontes , de Melo Lucília Vilela , Beppu Marisa Massumi , Breitkreitz Márcia Cristina , Santana Cesar Costapinto
Published: August 2017

In this study, an analytical method based on Design of Experiments and response surface methodology for the separation of lycopene, beta‐carotene, coenzyme Q10, and lutein was developed by ultra‐high performance supercritical fluid chromatography technique. A Central Composite Design was used to evaluate the influence of temperature, pressure, and ethanol percentage on the retention and separation factors of these compounds. In the designed experiments, the temperature was varied between 25 and 50 °C (298 and 323 K), the pressure within the interval of 1500 and 2200 psi (10 and 15 MPa), and the ethanol percentage between 15 and 24 (v/v) %. Each variable was tested at 3 levels and 5 replicated central points were added. It was found for the studied system that the ethanol percentage and pressure were the parameters that most influenced the retention factors whereas the ethanol percentage, pressure, and temperature affected the separation factors. Quadratic models were necessary to describe the retention and separation of these compounds. Furthermore, interactions among the factors were observed, justifying the DOE approach used in this work. Considering the retention and separation factors, the selected operating conditions for further experiments were: 15.5 % of ethanol at 40 °C (313 K) and 1500 psi (10 MPa).
A novel modulation technique with interleaved‐and‐shifted shoot‐through state placement for quasi‐Z‐source inverters
Authors: Wang Shun‐Chung , Liu Yi‐Hua , Cheng Yu‐Shan , Peng Bo‐Ruei
Published: August 2017

In this paper, a single‐phase quasi‐Z‐source (qZS) inverter (qZSI), integrating the pulse width modulation (PWM) control with interleaved‐and‐shifted shoot‐through state (STS) placement modulation technique, is proposed to simultaneously achieve both dc voltage boost and dc‐ac inversion. Instead of placing the STS in both inverter legs simultaneously, the addressed method inserts the STS only in left/right inverter leg separately during the positive/negative half cycle of the output voltage to reduce switching losses and thermal stresses of the power devices. The STS shift is also studied to decrease the switching numbers of power devices and thus can improve the efficiency further. Theoretical analysis and design guidelines of the studied inverter are included. Improvement in effectiveness and performance of the devised scheme and modulation strategy are proved experimentally and compared with the previous studies on a built laboratory prototype.
The combined application of urinary liquid‐based cytology with fluorescence in situ hybridization and p16/Ki‐67 dual immunostaining is valuable for improving the early diagnosis of upper tract urothelial carcinomas
Authors: Sun Xueqi , Liu Xubin , Xia Meng , Yang Shicong , Fei Lingyan , Zhang Mengqi , Ma Hanyu , Wang Liantang , Chen Shangwu , Yu Li
Published: August 2017

Objectives

To evaluate the diagnostic values of urine liquid‐based cytology (LBC), fluorescence in situ hybridization (FISH), and p16/Ki‐67 dual immunostaining in the detection of upper tract urothelial carcinomas (UTUCs).

Methods

Sixty‐one patients with UTUCs were retrospectively analyzed. All patients were diagnosed both by urine cytology and by FISH, and histologically confirmed as UTUCs. Thirty‐two patients had been stained with p16/Ki‐67 dual labeling.

Results

The sensitivities for low‐grade UTUCs (LGUTUCs) and high‐grade UTUCs (HGUTUCs) were 33.3% and 67.4% by LBC, 60% and 69.6% by FISH, and 12.5% and 66.7% by p16/Ki‐67 dual labeling, respectively.

Conclusions

Our results indicated that LBC was more suitable to identify HGUTUCs, FISH was highly valuable for predicting LGUTUCs, and p16/Ki‐67 dual labeling was useful for distinguishing HGUTUCs from LGUTUCs. The combined application of these methods may improve the sensitivity or accuracy in the detection or diagnosis of UTUCs.
Symbiosis constraints: Strong mycobiont control limits nutrient response in lichens
Authors: Palmqvist Kristin , Franklin Oskar , Näsholm Torgny
Published: August 2017

Symbioses such as lichens are potentially threatened by drastic environmental changes. We used the lichen Peltigera aphthosa—a symbiosis between a fungus (mycobiont), a green alga (Coccomyxa sp.), and N2‐fixing cyanobacteria (Nostoc sp.)—as a model organism to assess the effects of environmental perturbations in nitrogen (N) or phosphorus (P). Growth, carbon (C) and N stable isotopes, CNP concentrations, and specific markers were analyzed in whole thalli and the partners after 4 months of daily nutrient additions in the field. Thallus N was 40% higher in N‐fertilized thalli, amino acid concentrations were twice as high, while fungal chitin but not ergosterol was lower. Nitrogen also resulted in a thicker algal layer and density, and a higher δ13C abundance in all three partners. Photosynthesis was not affected by either N or P. Thallus growth increased with light dose independent of fertilization regime. We conclude that faster algal growth compared to fungal lead to increased competition for light and CO2 among the Coccomyxa cells, and for C between alga and fungus, resulting in neither photosynthesis nor thallus growth responded to N fertilization. This suggests that the symbiotic lifestyle of lichens may prevent them from utilizing nutrient abundance to increase C assimilation and growth.
Predicting the establishment success of introduced target species in grassland restoration by functional traits
Authors: Engst Karina , Baasch Annett , Bruelheide Helge
Published: August 2017

Species‐rich semi‐natural grasslands are highly endangered habitats in Central Europe and numerous restoration efforts have been made to compensate for the losses in the last decades. However, some plant species could become more easily established than others. The establishment success of 37 species was analyzed over 6 years at two study sites of a restoration project in Germany where hay transfer and sowing of threshing material in combination with additional sowing were applied. The effects of the restoration method applied, time since the restoration took place, traits related to germination, dispersal, and reproduction, and combinations of these traits on the establishment were analyzed. While the specific restoration method of how seeds were transferred played a subordinate role, the establishment success depended in particular on traits such as flower season or the lifeform. Species flowering in autumn, such as Pastinaca sativa and Serratula tinctoria, became established better than species flowering in other seasons, probably because they could complete their life cycle, resulting in increasingly stronger seed pressure with time. Geophytes, like Allium angulosum and Galium boreale, became established very poorly, but showed an increase with study duration. For various traits, we found significant trait by method and trait by year interactions, indicating that different traits promoted establishment under different conditions. Using a multi‐model approach, we tested whether traits acted in combination. For the first years and the last year, we found that models with three traits explained establishment success better than models with a single trait or two traits. While traits had only an additive effect on the establishment success in the first years, trait interactions became important thereafter. The most important trait was the season of flowering, which occurred in all best models from the third year onwards. Overall, our approach revealed the potential of functional trait analysis to predict success in restoration projects.
Rhododendron aureum Georgi formed a special soil microbial community and competed with above‐ground plants on the tundra of the Changbai Mountain, China
Authors: Wang Xiaolong , Li Lin , Zhao Wei , Zhao Jiaxin , Chen Xia
Published: August 2017

Rhododendron aureum Georgi is a perennial evergreen dwarf shrub that grows at all elevations within the alpine tundra of northern China. Previous research has investigated the plant communities of R. aureum; however, little information is available regarding interspecific competition and underground soil microbial community composition. The objective of our study was to determine whether the presence of R. aureum creates a unique soil microbiome and to investigate the relationship between R. aureum and other plant species. Our study site ranged from 1,800 to 2,600 m above sea level on the northern slope of the Changbai Mountain. The results show that the soil from sites with an R. aureum community had a higher abundance of nitrogen‐fixing bacteria and a higher resistance to pathogens than soils from sites without R. aureum. We emphasize that R. aureum promotes a unique soil microbial community structure that is distinct from those associated with other plants. Elevation and microbial biomass were the main influencing factors for plant community structure. Analysis of interspecific relationships reveals that R. aureum is negatively associated with most other dominant shrubs and herbs, suggesting interspecific competition. It is necessary to focus on other dominant species if protection and restoration of the R. aureum competition is to occur. In the future, more is needed to prove whether R. aureum decreases species diversity in the tundra ecosystems of Changbai Mountain.
Human dendritic cells activated with MV130 induce Th1, Th17 and IL‐10 responses via RIPK2 and MyD88 signalling pathways
Authors: Cirauqui Cristina , Benito‐Villalvilla Cristina , Sánchez‐Ramón Silvia , Sirvent Sofía , Diez‐Rivero Carmen M. , Conejero Laura , Brandi Paola , Hernández‐Cillero Lourdes , Ochoa Juliana Lucía , Pérez‐Villamil Beatriz , Sancho David , Subiza José Luis , Palomares Oscar
Published: August 2017

Recurrent respiratory tract infections (RRTIs) are the first leading cause of community‐ and nosocomial‐acquired infections. Antibiotics remain the mainstay of treatment, enhancing the potential to develop antibiotic resistances. Therefore, the development of new alternative approaches to prevent and treat RRTIs is highly demanded. Daily sublingual administration of the whole heat‐inactivated polybacterial preparation (PBP) MV130 significantly reduced the rate of respiratory infections in RRTIs patients, however, the immunological mechanisms of action remain unknown. Herein, we study the capacity of MV130 to immunomodulate the function of human dendritic cells (DCs) as a potential mechanism that contribute to the clinical benefits. We demonstrate that DCs from RRTIs patients and healthy controls display similar ex vivo immunological responses to MV130. By combining systems biology and functional immunological approaches we show that MV130 promotes the generation of Th1/Th17 responses via receptor‐interacting serine/threonine‐protein kinase‐2 (RIPK2)‐ and myeloid‐differentiation primary‐response gene‐88 (MyD88)‐mediated signalling pathways under the control of IL‐10. In vivo BALB/c mice sublingually immunized with MV130 display potent systemic Th1/Th17 and IL‐10 responses against related and unrelated antigens. We elucidate immunological mechanisms underlying the potential way of action of MV130, which might help to design alternative treatments in other clinical conditions with high risk of recurrent infections.
Efficient Phosphorescence from Naphthalenebenzimidizole‐Coordinated Iridium(III) Chromophores
Authors: Yarnell James E. , De La Torre Patricia , Castellano Felix N.
Published: August 2017

The electronic structure and photophysical properties of two phosphorescent iridium(III) cyclometalated complexes are presented. The molecules were synthesized by cyclometalating the ligand 1,8‐naphthalenebenzimidizole (NBI), to an iridium(III) metal center. Two NBI ligands were covalently attached along with a 1,10‐phenanthroline (phen) ligand producing the [Ir(NBI)2(phen)](PF6) complex and three NBI ligands were used to prepare the corresponding tris‐cyclometalate fac‐Ir(NBI)3. The optical properties of these new IrIII molecules were investigated using DFT calculations, photoluminescence spectroscopy, and transient absorption spectroscopy. The molecules at the heart of this study were found to contain long‐lived ligand‐localized triplet excited states on the NBI species, featuring energies suitable for bimolecular photochemical reactions. Both iridium(III) chromophores possess excellent light absorptivity in the visible region of the spectrum with high photoluminescence quantum efficiencies approaching 30 %.
Luminescent PtII Complexes of Tridentate Cyclometalating 2,5‐Bis(aryl)‐pyridine Ligands
Authors: Krause Maren , Kourkoulos Dimitrios , González‐Abradelo Darío , Meerholz Klaus , Strassert Cristian A. , Klein Axel
Published: August 2017

Bis‐cyclometalated PtII complexes of dianionic 2,5‐bis(aryl)‐pyridine ligands (L1–6)2–, carrying various cyclometalating or pending aryl groups, are synthesised in two steps. The reactions of H2L protoligands with K2[PtCl4] in acetic acid give the mono‐cyclometalated complexes [Pt(HL)Cl]2. Heating these complexes in hot DMSO (dimethyl sulfoxide) yields the double‐cyclometalated DMSO complexes [Pt(L1–6)(DMSO)]. The reaction of [Pt(L4)(DMSO)] with N,N‐dimethylimidazolium iodide in the presence of KOtBu as the base gives the carbene complex [Pt(L4)(Me2Imd)]. Detailed photophysical studies reveal the intense orange luminescence of these complexes in CH2Cl2 solution, with quantum yields up to 0.22, and increased quantum yields of up to 1.00 in glassy frozen CH2Cl2/MeOH (1:1) and up to 0.44 in PMMA matrices. Detailed electrochemistry (including spectroelectrochemistry) reveals reversible ligand‐based first reductions at –2.1 to –2.3 V, irreversible Pt‐centred oxidations at around 0.8 V and electrochemical band gaps of 2.8–3.0 eV. Further reduction waves at very negative potentials interfere with the solvent (THF with traces of water) discharge and can be traced, with UV/Vis spectroelectrochemistry, to Pt‐centred reductions for the DMSO complexes and to a second ligand‐centred reduction for the Me2Imd complex from. The photo/electrochemical properties can be roughly correlated with the ligand pattern and suggest their use in optoelectronic applications.
[6]–[9]Metacyclophanes: Synthesis, Crystal Structures, and NMR and UV Spectroscopy
Authors: Shuvalov Vladislav Yu. , Eltsov Ilia V. , Tumanov Nikolay A. , Boldyreva Elena V. , Nefedov Andrey A. , Sagitullina Galina P.
Published: August 2017

Metacyclophanes have been developed as non‐planar aromatic compounds with unusual physical properties. [6]–[9]Metacyclophanes were synthesized by rearrangement of 3‐nitro(perhydrocycloalka)[b]pyridinium salts, and analysis of their spectroscopic data and X‐ray diffraction patterns indicates the aromaticity and flexibility of their benzene rings. The effectiveness and simplicity of the synthesis makes it possible to use them as available precursors in the synthesis of retinoids, indolophanes, and carbazolophanes.
The Manganese‐Catalyzed Cross‐Coupling Reaction and the Influence of Trace Metals
Authors: Santilli Carola , Beigbaghlou Somayyeh Sarvi , Ahlburg Andreas , Antonacci Giuseppe , Fristrup Peter , Norrby Per‐Ola , Madsen Robert
Published: August 2017

The substrate scope of the MnCl2‐catalyzed cross‐coupling between aryl halides and Grignard reagents has been extended to several methyl‐substituted aryl iodides by performing the reaction at elevated temperature in a microwave oven. A radical clock experiment revealed the presence of an aryl radical as an intermediate leading to the proposal of an SRN1 pathway for the coupling. The mechanistic information gave rise to suspicion about two previously published cross‐coupling reactions catalyzed by manganese(II) salts. As a result, the coupling between aryl halides and organostannanes as well as between aryl halides and amines were revisited. Both reactions were found impossible to reproduce without the addition of small amounts of palladium or copper and are therefore not believed to be catalyzed by manganese.
Effects of Substituents on the Electrocatalytic Activity of Cobalt Phthalocyanines when Conjugated to Graphene Quantum Dots
Authors: Centane Sixolile , Achadu Ojodomo J. , Nyokong Tebello
Published: August 2017

We report on the π–π interactions between graphene quantum dots (GQDs) and the following cobalt phthalocyanine derivatives: cobalt monocarboxyphenoxy phthalocyanine (complex 1), cobalt tetracarboxyphenoxyphthalocyanine (complex 2), and cobalt tetraaminophenoxy phthalocyanine (complex 3). The conjugates (conj) with GQDs are represented as 1@GQDs(conj), 2@GQDs(conj) and 3@GQDs(conj), respectively. The resulting phthalocyanine/GQDs conjugates were adsorbed on containing a glassy carbon electrode (GCE) using the drop and dry method. We explore the electrochemical properties of phthalocyanines functionalized with both electron withdrawing groups and electron donating groups when non‐covalently linked to the π‐electron rich graphene quantum dots. GCE/3, GCE/2@GQDs(conj) and GCE/1@GQDs(conj) had the lowest limits of detection (LOD). Sequentially modified electrodes showed less favourable detection limits compared to the conjugates.
Neuropsychological and Cognitive Correlates of Recovery in Anorexia Nervosa
Authors: Harper Jessica A. , Brodrick Brooks , Van Enkevort Erin , McAdams Carrie J.
Published: August 2017

Objective

To identify clinical or cognitive measures either predictive of illness trajectory or altered with sustained weight recovery in adult women with anorexia nervosa.

Methods

Participants were recruited from prior studies of women with anorexia nervosa (AN‐C) and in weight‐recovery following anorexia nervosa (AN‐WR). Participants completed a neuropsychological battery at baseline and clinical assessments at both baseline and follow‐up. Groups based on clinical outcome (continued eating disorder, AN‐CC; newly in recovery, AN‐CR; sustained weight‐recovery, AN‐WR) were compared by using one‐way ANOVAs with Bonferroni‐corrected post hoc comparisons.

Results

Women with continued eating disorder had poorer neuropsychological function and self‐competence at baseline than AN‐CR. AN‐CR showed changes in depression and externalizing bias, a measure of self‐related attributions. AN‐WR differed from both AN‐CC and AN‐CR at baseline in externalizing bias, but only from AN‐CC at outcome.

Discussion

Neuropsychological function when recently ill may be a prognostic factor, while externalizing bias may provide a clinical target for recovery. Copyright © 2017 John Wiley & Sons, Ltd and Eating Disorders Association.