bluuebunny/crossref_metadata_2025 huggingface dataset:
Shape‐Dependent Electrocatalysis: Oxygen Reduction on Carbon‐Supported Gold Nanoparticles
Authors: Erikson Heiki , Sarapuu Ave , Tammeveski Kaido , Solla‐Gullón Jose , Feliu Juan M.
Published: July 2014

Cubic, octahedral and quasi‐spherical (two different particle sizes) Au nanoparticles are synthesised and dispersed in a carbon‐black powder. The size and morphology of the Au nanocatalysts is confirmed by transmission electron microscopy and X‐ray diffraction. Au nanospheres are approximately 5 and 30 nm in diameter, whereas the size of Au octahedra and nanocubes is approximately 40–45 nm. The electrocatalytic activity of these carbon‐supported particles towards the oxygen reduction reaction (ORR) is studied in 0.5 M H2SO4 and 0.1 M KOH solutions by using the rotating‐disk‐electrode method. The specific activity (SA) for O2 reduction is measured, and the highest SA is observed for Au nanocubes supported on carbon. The highest mass activities are found for the smallest Au nanoparticles. Tafel analysis suggests that the mechanism of the ORR on shape‐controlled Au/C catalysts is the same as on bulk Au.
Effects of Redox Mediators on the Catalytic Activity of Iron Porphyrins towards Oxygen Reduction in Acidic Media
Authors: He Qinggang , Wu Gang , Liu Ke , Khene Samson , Li Qing , Mugadza Tawanda , Deunf Elise , Nyokong Tebello , Chen Shaowei W.
Published: July 2014

The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso‐tetra(N‐methyl‐4‐pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half‐wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′‐azino‐bis(3‐ethylbenzothiazioline‐6‐sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron‐transfer kinetics were also evaluated.
Vibrational Spectrum and Gas‐Phase Structure of Disulfur Dinitride (S2N2)
Authors: Perrin Agnes , Flores Antognini Andrea , Zeng Xiaoqing , Beckers Helmut , Willner Helge , Rauhut Guntram
Published: July 2014

Gas‐phase FTIR spectra of the ν6(B‐type) and the ν4(C‐type) fundamental bands of S2N2(D2h) were recorded with a resolution of ≤0.004 cm−1and the vibrational spectrum of S2N2(D2h) in solid Ar has been revisited. All IR‐active fundamentals and four combination bands were assigned in excellent agreement with calculated values from anharmonic VPT2 and VCI theory based on (explicitly correlated) coupled‐cluster surfaces. Accurate experimental vibrational ground‐ and excited‐state rotational constants of32S214N2are obtained from a rovibrational analysis of the ν6and ν4fundamental bands, and precise zero‐point average rz(Rz(SN)=1.647694(95) Å,αz(NSN)=91.1125(33)°) and semi‐experimental equilibrium structures (Re(SN)=1.64182(33) Å,αe(NSN)=91.0716(93)°) of S2N2have been established. These are compared to the solid‐state structure of S2N2and structural properties of related sulfur nitrogen compounds and to results of ab initio structure calculations.
Discrimination between Olfactory Receptor Agonists and Non‐agonists
Authors: Topin Jérémie , de March Claire A. , Charlier Landry , Ronin Catherine , Antonczak Serge , Golebiowski Jérôme
Published: July 2014

A joint approach combining free‐energy calculations and calcium‐imaging assays on the broadly tuned human 1G1 olfactory receptor is reported. The free energy of binding of ten odorants was computed by means of molecular‐dynamics simulations. This state function allows separating the experimentally determined eight agonists from the two non‐agonists. This study constitutes a proof‐of‐principle for the computational deorphanization of olfactory receptors.
Direct Trifluoromethylthiolation of Alcohols under Mild Reaction Conditions: Conversion of ROH into RSCF3
Authors: Nikolaienko Pavlo , Pluta Roman , Rueping Magnus
Published: July 2014

A direct process for the trifluoromethylthiolation of allylic and benzylic alcohols under mild conditions has been developed. A wide range of free alcohols underwent nucleophilic substitution in the presence of stable CuSCF3 and BF3⋅Et2O to give the corresponding products in good to excellent yields.
Design of Fluorescent Nanocapsules as Ratiometric Nanothermometers
Authors: Zhegalova Natalia G. , Dergunov Sergey A. , Wang Steven T. , Pinkhassik Eugene , Berezin Mikhail Y.
Published: July 2014

We have developed a novel design of optical nanothermometers that can measure the surrounding temperature in the range of 20–85 °C. The nanothermometers comprise two organic fluorophores encapsulated in a crosslinked polymethacrylate nanoshell. The role of the nanocapsule shell around the fluorophores is to form a well‐defined and stable microenvironment to prevent other factors besides temperature from affecting the dyes’ fluorescence. The two fluorophores feature different temperature‐dependent emission profiles; a fluorophore with relatively insensitive fluorescence (rhodamine 640) serves as a reference whereas a sensitive fluorophore (indocyanine green) serves as a sensor. The sensitivity of the nanothermometers depends on the type of nanocapsule‐forming lipid and is affected by the phase transition temperature. Both the fluorescence intensity and the fluorescence lifetime can be utilized to measure the temperature.
Gold‐Catalyzed Oxa‐Povarov Reactions for the Synthesis of Highly Substituted Dihydrobenzopyrans from Diaryloxymethylarenes and Olefins
Authors: Pagar Vinayak Vishnu , Tseng Chang‐Chin , Liu Rai‐Shung
Published: July 2014

Oxa‐Povarov reactions involving readily available diaryloxymethylarenes and aryl‐substituted alkenes are reported. Their [4+2] cycloadditions were efficiently catalyzed by IPrAuSbF6 (IPr=1,3‐bis(diisopropylphenyl)imidazol‐2‐ylidene) with high diastereoselectivity. Product analysis revealed that the reactions likely proceed by a stepwise ionic mechanism, because both E‐ and Z‐configured β‐methylstyrene gave the same cycloadducts in the same proportions.
Can Low‐Valent Germanium Chemistry Be Practiced Under Ambient Conditions? A Tale of a Water‐Stable Yet Reactive Germylene Monochloride Complex
Authors: Jha Chandan Kumar , Karwasara Surendar , Nagendran Selvarajan
Published: July 2014

A germylene monochloride complex ((DPM)GeCl, 1) that is water stable was isolated for the first time. Interestingly, it reacts with cesium fluoride under ambient conditions (non‐inert atmosphere and water‐containing solvent) to afford water stable germylene monofluoride complex ((DPM)GeF, 2). Due to the usage of DPM (dipyrrinate) ligand, germylene monohalides 1 and 2 show fluorescence in the visible region at 555 and 538 nm, respectively. Compounds 1 and 2 are the first fluorescent germylene complexes and were characterized by multinuclear NMR spectroscopy. The structure of compound 1 was also proved by single crystal X‐ray diffraction studies.
Disupersilylperoxo Radical Anion [tBu3SiOOSitBu3]⋅−: An Intermediate of Supersilanide Oxidation
Authors: Budanow Alexandra , Haeri Haleh Hashemi , Sänger Inge , Schödel Frauke , Bolte Michael , Prisner Thomas , Wagner Matthias , Lerner Hans‐Wolfram
Published: July 2014

In the oxidative process of the supersilanide anion [SitBu3]−, radical species are generated. The continuous wave (cw)‐EPR spectrum of the reaction solution of Na[SitBu3] with O2 revealed a signal, which could be characterized as disupersilylperoxo radical anion [tBu3SiOOSitBu3]⋅− affected by sodium ions though ion‐pair formation. A mechanism is suggested for the oxidative process of supersilanide, which in a further step can be helpful in a better understanding of the oxidation process of isoelectronic phosphanes.
Synthesis and Photophysics of a Red‐Light Absorbing Supramolecular Chromophore System
Authors: Rombouts Jeroen A. , Ravensbergen Janneke , Frese Raoul N. , Kennis John T. M. , Ehlers Andreas W. , Slootweg J. Chris , Ruijter Eelco , Lammertsma Koop , Orru Romano V. A.
Published: July 2014

Invited for the cover of this issue is the group of Romano V. A. Orru and Koop Lammertsma at the VU University of Amsterdam. The image depicts the photoexcitation of the aromatic core of a red‐light absorbing supramolecular chromophore system. Read the full text of the article at 10.1002/chem.201402398.
Performance of Surfactant Assisted Synthesis of Fe/TiO2 on the Photodegradation of Diisopropanolamine
Authors: Ramli Raihan Mahirah , Chong Fai Kait , Omar Abdul Aziz , Murugesan Thanapalan
Published: July 2014

Titanium dioxide, TiO2 nanoparticles were synthesized via microemulsion method employing Triton X‐100 as the surfactant. Heat treatment was used to remove residual organic entities and also to produce anatase TiO2. Iron (Fe) was incorporated by wet impregnation into the TiO2 nanoparticles in order to shift the active region of the photocatalyst from UV into visible region. The Fe/TiO2 photocatalyst was characterized and their performance on the degradation of aqueous diisopropanolamine solution was compared with the commercial TiO2. The optimum conditions for the photodegradation of aqueous diisopropanolamine were found to be at 0.2 wt% of Fe. The present synthesized Fe/TiO2 photocatalyst showed an improved performance over the commercial TiO2 on the COD removal.
The Role of Environmental and Spatial Processes in Structuring Stream Macroinvertebrates Communities in a Large River Basin
Authors: Wan Yun , Xu Lili , Hu Jin , Xu Chi , Wan An , An Shuqing , Chen Yushun
Published: July 2014

Understanding spatial patterns of stream biological communities is important for stream ecosystem management. The questions which variables (spatial variables vs. environmental variables) are driving stream community structure, and whether stream network configuration could influence spatial patterns of the structure, are less investigated. We used stream macroinvertebrates community and environmental data collected from 142 sites in August 2010 across the Huai River basin, China, to answer these questions. Spatial variables were constructed based on symmetrical Euclidean distance and stream distance by using Moran's eigenvector maps. We evaluated the relative impacts of local environmental (physicochemical variables) and spatial (generated by overland and watercourse distances among sites) variables on the structure of macroinvertebrates using variation partitioning methods. Our results showed that both space and environment had significant effects on macroinvertebrates community composition, and the former explained more variations. Moreover, spatial variables based on the watercourse distance captured slightly more variation of macroinvertebrates community in stream networks than those derived from the overland distance.
The Age, Growth, Fecundity ofCarassius auratusin the Guohe River of Guoyang County
Authors: Wan An , Yu Shijin , Hu Jin , Wan Yun , Wei Ying , Zhong Ming , Yang Hongfei , An Shuqing , Yan Yunzhi
Published: July 2014

To assess the water quality of the Guohe River, the age, growth, and fecundity ofCarassius auratusin the Guohe River were studied. It was found that the species consists of groups aged one and two with a sex ratio of 30.67:1 (females/males) –C. auratushas the first sexual maturity at the age of one (the year after being hatched). The power function relationship existed between total length (TL) and total or somatic weight (TW, SW). The TL–TW equations for the whole group was TW = 0.0021 TL2.6392(R2 = 0.9301,p < 0.01), and the TL–SW equations for the whole group was SW = 0.0027 TL2.4164(R2 = 0.936,p < 0.01), respectively. The individual absolute fecundity was 28 151 eggs. And the relative fecundity was 148.84 eggs/g fish. A linear relationship existed between the absolute fecundity and the total weight. All results showed that there was a suitable environment for the survival ofC. auratusin the water area. But in an unstable situation the feralC. auratuspopulation revealed an “exploitation” pattern with younger age, more female, and higher fecundity in the Guohe River, which may have mainly been caused by serious paroxysmal pollution accidents.
Increase in testicular germ cell tumor incidence among Hispanic adolescents and young adults in the United States
Authors: Chien Franklin L. , Schwartz Stephen M. , Johnson Rebecca H.
Published: July 2014

BACKGROUND

Although rising incidence rates of testicular germ cell tumors have been well documented in white men, relatively little is known about rates in men of Hispanic origin. In the current study, the authors compared germ cell tumor trends between men of Hispanic and non‐Hispanic origin as a function of age at diagnosis.

METHODS

Trends in testicular germ cell tumor incidence among white men were analyzed according to Hispanic ethnicity in 2 data sets of the National Cancer Institute's Surveillance, Epidemiology, and End Results Program, spanning from 1992 to 2010 and from 2000 to 2010 and sampling 15% and 28% of the United States population, respectively. Rates were age‐adjusted to the year 2000 US standard population.

RESULTS

Between 1992 and 2010, the annual incidence of testicular germ cell tumors among Hispanic whites ages 15 to 39 years increased 58%, from 7.18 cases per 100,000 in 1992 to 11.34 cases per 100,000 by 2010 (P<1 × 10−9). Their incidence rates increased in metropolitan areas for both seminoma and nonseminoma subtypes and for all stages at diagnosis. During the same 19‐year interval, incidence among non‐Hispanic white young adults increased 7%, from 12.41 to 13.22 per 100,000. During the 2000 to 2010 interval, no significant trends were observed in incidence among non‐Hispanic whites.

CONCLUSIONS

There has been a recent substantial increase in testicular germ cell tumor incidence among Hispanic adolescents and young adults in the United States. Similar trends were not observed in non‐Hispanic whites. Cancer 2014;120:2728–2734. © 2014 American Cancer Society.
Polymorphisms in folate‐metabolizing enzymes and response to 5‐fluorouracil among patients with stage II or III rectal cancer (INT‐0144; SWOG 9304)
Authors: Ulrich Cornelia M. , Rankin Cathryn , Toriola Adetunji T. , Makar Karen W. , Altug‐Teber Özge , Benedetti Jacqueline K. , Holmes Rebecca S. , Smalley Stephen R. , Blanke Charles D. , Lenz Heinz‐Josef
Published: July 2014

BACKGROUND

Recurrence and toxicity occur commonly among patients with rectal cancer who are treated with 5‐fluorouracil (5‐FU). The authors hypothesized that genetic variation in folate‐metabolizing genes could play a role in interindividual variability. The objective of the current study was to evaluate the associations between genetic variants in folate‐metabolizing genes and clinical outcomes among patients with rectal cancer treated with 5‐FU.

METHODS

The authors investigated 8 functionally significant polymorphisms in 6 genes (methylenetetrahydrofolate reductase [MTHFR] [C677T, A1298C], SLC19A1 [G80A], SHMT1 [C1420T], dihydrofolate reductase [DHFR] [Del19bp], TS 1494del,and TSER) involved in folate metabolism in 745 patients with TNM stage II or III rectal cancer enrolled in a phase 3 adjuvant clinical trial of 3 regimens of 5‐FU and radiotherapy (INT‐0144 and SWOG 9304).

RESULTS

There were no statistically significant associations noted between polymorphisms in any of the genes and overall survival, disease‐free survival (DFS), and toxicity in the overall analyses. Nevertheless, there was a trend toward worse DFS among patients with the variant allele of MTHFR C677T compared with wild‐type, particularly in treatment arm 2, in which patients with the MTHFR C677T TT genotype had worse overall survival (hazards ratio, 1.76; 95% confidence interval, 1.06‐2.93 [P = .03]) and DFS (hazards ratio, 1.84; 95% confidence interval, 1.12‐3.03 [P = .02]) compared with those with homozygous wild‐type. In addition, there was a trend toward reduced hematological toxicity among patients with variants of SLC19A1 G80A in treatment arm 1 (P for trend, .06) and reduced esophagitis/stomatitis noted among patients with variants of TSER in treatment arm 3 (P for trend, .06).

CONCLUSIONS

Genetic variability in folate‐metabolizing enzymes was found to be associated only to a limited degree with clinical outcomes among patients with rectal cancer treated with 5‐FU. Cancer 2014;120:3329–3337. © 2014 American Cancer Society.
Does adjuvant radiotherapy benefit patients with diffuse‐type gastric cancer? Results from the Surveillance, Epidemiology, and End Results database
Authors: Stessin Alexander M. , Sison Cristina , Schwartz Allie , Ng John , Chao Clifford K.S. , Li Baoqing
Published: July 2014

BACKGROUND

Diffuse‐type gastric cancer is observed in approximately one‐third of gastric cancers, yet the optimal treatment remains controversial. In the recently published Intergroup 0116 trial, a subgroup analysis demonstrated a lack of a long‐term survival benefit for adjuvant chemoradiation therapy among patients with diffuse‐type gastric cancer.

METHODS

The Surveillance, Epidemiology, and End Results registry database was queried for patients who were newly diagnosed with diffuse‐type gastric cancer between 2002 and 2005 and underwent surgical resection with or without adjuvant radiotherapy (RT). Overall survival (OS) was analyzed by the Kaplan‐Meier method. Cox proportional hazards models were used to investigate the association between adjuvant RT and OS, with and without adjusting for other factors. In addition, propensity score methods were used to control for the possible effects of measured confounders.

RESULTS

A total of 1889 cases of surgically resected diffuse‐type gastric cancer were included in the analysis; of these cases, 782 patients received adjuvant RT and 1107 did not receive RT. The median survival time was 30 months in the group treated with adjuvant RT versus 18 months in the group that did not receive RT with matched propensity scores (P<.001). The Cox model confirmed the improvement in OS in patients who received adjuvant RT (hazard ratio, 0.75; 95% confidence interval, 0.65‐0.82 [P<.001]).

CONCLUSIONS

The current population‐based observational study suggested a potential survival benefit for adjuvant RT among patients with diffuse‐type gastric cancer. The standard treatment will likely remain controversial until evidence becomes available from phase 3 randomized trials exclusively for patients with diffuse‐type gastric cancer. Cancer 2014;120:3562–3568. © 2014 American Cancer Society.
A randomized, open‐label 3‐way crossover study to investigate the relative bioavailability and bioequivalence of crushed sildenafil 20 mg tablets mixed with apple sauce, extemporaneously prepared suspension (EP), and intact sildenafil 20 mg tablets in healthy volunteers under fasting conditions
Authors: Gao Xiang , Ndongo Marie‐Noella , Checchio Tina M. , Cook Jack , Duncan Barbara , LaBadie Robert R.
Published: July 2014

The relative bioavailability and bioequivalence of 20‐mg doses of a pediatric formulation of sildenafil extemporaneous preparation suspension (EP; 10 mg/mL), the sildenafil 20‐mg intact tablet and the crushed sildenafil 20‐mg tablet mixed with apple sauce were assessed in a single‐dose, randomized, open‐label, 3‐way crossover study with 18 healthy adult volunteers. Blood samples were collected at predefined times and analyzed for sildenafil plasma concentrations. Natural log‐transformed sildenafil pharmacokinetic parameters (Cmax, AUClast, and AUCinf) were used to estimate relative bioavailability and construct 90% confidence intervals (CI) using a mixed‐effects model. Bioequivalence was concluded among the three formulations with one exception, in which the EP suspension showed a 15% decrease in Cmax with a lower 90% CI of 76% compared with the intact tablet. The 15% decrease in sildenafil Cmax is not considered to be clinically relevant. Therefore, the EP suspension is considered to be an appropriate pediatric formulation. All 3 formulations were well tolerated in healthy adult volunteers.
Managing resources dynamically in hybrid photonic‐electronic networks‐on‐chip
Authors: García‐Guirado Antonio , Fernández‐Pascual Ricardo , García José M. , Bartolini Sandro
Published: July 2014

Nanophotonics promises to solve the scalability problems of current electrical interconnects thanks to its low sensitivity to distance in terms of latency and energy consumption. Before this technology reaches maturity, hybrid photonic‐electronic networks will be a viable alternative. Ideally, ordinary electrical meshes and ring‐based photonic networks should cooperate to minimize overall latency and energy consumption, but currently, we lack mechanisms to do this efficiently. In this paper, we present novel fine‐grain policies to manage the photonic resources in a tiled chip multiprocessor (CMP) scenario. Our policies are dynamic and base their decisions on parameters such as message size, ring availability, and distance between endpoints, at the message level. The resulting network behavior is also fairer to all cores, reducing processor idle time thanks to faster thread synchronization. All these policies improve performance when compared to the same CMP without the photonic ring, and the most elaborate ones reduce the overall network latency by 50%, execution time by 36%, and network energy consumption by 52% on average, in a 16‐core CMP for the PARSEC benchmark suite. Larger hybrid networks with 64 endpoints for 256‐core CMPs, based on Corona and Firefly designs, also show far superior throughput and lower latency if managed by one of the proposed policies. Copyright © 2014 John Wiley & Sons, Ltd.
Modeling and optimizing MapReduce programs
Authors: Dörre Jens , Apel Sven , Lengauer Christian
Published: July 2014

MapReduce frameworks allow programmers to write distributed, data‐parallel programs that operate on multisets. These frameworks offer considerable flexibility to support various kinds of programs and data. To understand the essence of the programming model better and to provide a rigorous foundation for optimizations, we present an abstract, functional model of MapReduce along with a number of customization options. We demonstrate that the MapReduce programming model can also represent programs that operate on lists, which differ from multisets in that the order of elements matters. Along with the functional model, we offer a cost model that allows programmers to estimate and compare the performance of MapReduce programs. Based on the cost model, we introduce two transformation rules aiming at performance optimization of MapReduce programs, which also demonstrates the usefulness of our model. In an exploratory study, we assess the impact of applying these rules to two applications. The functional model and the cost model provide insights at a proper level of abstraction into why the optimization works. Copyright © 2014 John Wiley & Sons, Ltd.
Analysis of time delay difference due to parametric mismatch in matched filter channels
Authors: Stuarts Guillermo , Julián Pedro
Published: July 2014

This paper presents an analysis of the time delay difference between the outputs of two matched filter channels, in the presence of parametric mismatch. A theorem for computing the cross‐correlation value between two signals is developed. From the cross‐correlation theorem, expressions are developed that estimate the effect of parametric mismatch in the differential time delay (DTD) for filters of arbitrary type and order and input signals of arbitrary form. The accuracy of these expressions is simulated and then demonstrated experimentally using a carefully designed setup. Filter design considerations that attempt to minimize spurious DTD in high‐precision time delay estimation systems are presented. Copyright © 2014 John Wiley & Sons, Ltd.
Efficient optimization‐oriented design methodology of high‐order 3‐D filters using 2‐D and 3‐D electromagnetic simulators
Authors: Hinojosa J. , Quesada‐Pereira F. D. , Bozzi M. , Alvarez‐Melcon A.
Published: July 2014

This paper proposes a computationally highly efficient interface between two‐dimensional (2‐D) and three‐dimensional (3‐D) electromagnetic (EM) simulators for the optimization‐oriented design of high‐order 3‐D filters. In a first step, the novel optimization‐oriented design methodology aligns the 3‐D EM simulator response with the 2‐D EM simulator response of a low‐order 3‐D filter by using an inverse linear space mapping optimization technique. Then, a second mapping performs a calibration with the optimal 2‐D and 3‐D design parameters obtained from the first mapping. The optimization of high‐order filters is carried out using only the efficient 2‐D EM simulator, and the calibration equations directly give the design parameters of the 3‐D filter. The potential and the effectiveness of the proposed optimization‐oriented design methodology are demonstrated through the design of C‐band 3‐D evanescent rectangular waveguide bandpass filters with increasing orders from three to eight. Copyright © 2014 John Wiley & Sons, Ltd.
Long‐term colonization ecology of forest‐dwelling species in a fragmented rural landscape – dispersal versus establishment
Authors: Lõhmus Kertu , Paal Taavi , Liira Jaan
Published: July 2014

Species colonization in a new habitat patch is an efficiency indicator of biodiversity conservation. Colonization is a two‐step process of dispersal and establishment, characterized by the compatibility of plant traits with landscape structure and habitat conditions. Therefore, ecological trait profiling of specialist species is initially required to estimate the relative importance of colonization filters. Old planted parks best satisfy the criteria of a newly created and structurally matured habitat for forest‐dwelling plant species. We sampled species in 230 ancient deciduous forests (source habitat), 74 closed‐canopy manor parks (target habitats), 151 linear wooded habitats (landscape corridors), and 97 open habitats (isolating matrix) in Estonia. We defined two species groups of interest: forest (107 species) and corridor specialists (53 species). An extra group of open habitat specialists was extracted for trait scaling. Differing from expectations, forest specialists have high plasticity in reproduction mechanisms: smaller seeds, larger dispersules, complementary selfing ability, and diversity of dispersal vectors. Forest specialists are shorter, less nutrient‐demanding and mycorrhizal‐dependent, stress‐tolerant disturbance‐sensitive competitors, while corridor specialists are large‐seeded disturbance‐tolerant competitors. About 40% of species from local species pools have immigrated into parks. The historic forest area, establishment‐related traits, and stand quality enhance the colonization of forest specialists. The openness of landscape and mowing in the park facilitate corridor specialists. Species traits in parks vary between a forest and corridor specialist, except for earlier flowering and larger propagules. Forest species are not dispersal limited, but they continue to be limited by habitat properties even in the long term. Therefore, the shady parts of historic parks should be appreciated as important forest biodiversity‐enhancing landscape structures. The habitat quality of secondary stands can be improved by nurturing a heterogeneous shrub and tree layer, and modest herb layer management.
Comparison of Centralized and Decentralized Systems in Power System Restoration
Authors: Yokoyama Tsukasa , Nagata Takeshi
Published: July 2014

This paper proposes a multiagent approach to decentralized power system restoration for distribution system networks and presents a comparison of centralized and decentralized systems for power system restoration. Numerous studies have been conducted on power system restoration problems. From the viewpoint of system structures, this research can be divided into two categories: centralized systems and decentralized systems. In this study, we solve a power system restoration problem for a power distribution network by two different methods: mathematical programming (MIP) and the proposed multiagent‐based method (MAS). The proposed multiagent system consists of several distributing substation agents (DSAGs) and load agents (LAGs). An LAG corresponds to the customer load, and a DSAG supplies electricity to the LAG. From the simulation results, it can be seen that the proposed system can reach the right solution by making use of only local information and that the solution quality is better than that of the centralized system (MIP). This means that the proposed multiagent restoration system is a promising approach to larger scale distribution networks.
Production of IgG autoantibody requires expression of activation‐induced deaminase in early‐developing B cells in a mouse model of SLE
Authors: Umiker Benjamin R. , McDonald Gabrielle , Larbi Amma , Medina Carlos O. , Hobeika Elias , Reth Michael , Imanishi‐Kari Thereza
Published: July 2014

Systemic lupus erythematosus (SLE) is an autoimmune disease characterized by the presence of pathogenic IgG antinuclear antibodies. Pathogenic IgG autoantibody production requires B‐cell activation, leading to the production of activation‐induced deaminase (AID) and class switching of IgM genes to IgG. To understand how and when B cells are activated to produce these IgG autoantibodies, we studied cells from 564Igi, a mouse model of SLE. 564Igi mice develop a disease profile closely resembling that found in human SLE patients, including the presence of IgG antinucleic acid Abs. We have generated 564Igi mice that conditionally express an activation‐induced cytidine deaminase transgene (Aicdatg), either in all B cells or only in mature B cells. Here, we show that class‐switched pathogenic IgG autoantibodies were produced only in 564Igi mice in which AID was functional in early‐developing B cells, resulting in loss of tolerance. Furthermore, we show that the absence of AID in early‐developing B cells also results in increased production of self‐reactive IgM, indicating that AID, through somatic hypermutation, contributes to tolerance. Our results suggest that the pathophysiology of clinical SLE might also be dependent on AID expression in early‐developing B cells.
Patients with T+/low NK+ IL‐2 receptor γ chain deficiency have differentially‐impaired cytokine signaling resulting in severe combined immunodeficiency
Authors: Fuchs Sebastian , Rensing‐Ehl Anne , Erlacher Miriam , Vraetz Thomas , Hartjes Lara , Janda Ales , Rizzi Marta , Lorenz Myriam R. , Gilmour Kimberly , de Saint‐Basile Geneviève , Roifman Chaim M. , Cheuk Steven , Gennery Andrew , Thrasher Adrian J. , Fuchs Ilka , Schwarz Klaus , Speckmann Carsten , Ehl Stephan
Published: July 2014

X‐linked severe combined immunodeficiency (X‐SCID) leads to a T−NK−B+ immunophenotype and is caused by mutations in the gene encoding the IL‐2 receptor γ‐chain (IL2RG). IL2RGR222C leads to atypical SCID with a severe early onset phenotype despite largely normal NK‐ and T‐cell numbers. To address this discrepancy, we performed a detailed analysis of T, B, and NK cells, including quantitative STAT phosphorylation and functional responses to the cytokines IL‐2, IL‐4, IL‐15, and IL‐21 in a patient with the IL2RGR222C mutation. Moreover, we identified nine additional unpublished patients with the same mutations, all with a full SCID phenotype, and confirmed selected immunological observations. T‐cell development was variably affected, but led to borderline T‐cell receptor excision circle (TREC) levels and a normal repertoire. T cells showed moderately reduced proliferation, failing enhancement by IL‐2. While NK‐cell development was normal, IL‐2 enhancement of NK‐cell degranulation and IL‐15‐induced cytokine production were absent. IL‐2 or IL‐21 failed to enhance B‐cell proliferation and plasmablast differentiation. These functional alterations were reflected by a differential impact of IL2RGR222C on cytokine signal transduction, with a gradient IL‐4<IL‐2/IL‐15<IL‐21. Thus, IL2RGR222C causes a consistently severe clinical phenotype that is not predicted by the variable and moderate impairment of T‐cell immunity or TREC analysis.
Heteroleptic Pyridyl‐Carbene Iron Complexes with Tuneable Electronic Properties
Authors: Duchanois Thibaut , Etienne Thibaud , Beley Marc , Assfeld Xavier , Perpète Eric A. , Monari Antonio , Gros Philippe C.
Published: July 2014

New heteroleptic iron complexes mixing a terpyridine bearing a protonable pyridyl substituent (pytpy) and a pyridyl carbene ligand (carb) have been prepared and characterised by UV/Vis spectroscopy, cyclic voltammetry and TD‐DFT computations. The absorption spectrum of [Fe(carb)(pytpy)]2+ showed a notable redshift compared with the homoleptic [Fe(carb)2]2+ complex. The MLCT transition occurred at even lower energy when the pendant pyridine was protonated, leading to a wide absorption domain in the 450–650 nm range. Calculations revealed the strong propensity of excited electrons to move from the metal to the pytpy ligand in the complex. This new family of complexes is a promising addition to the arsenal of iron‐based chromophores with tuneable electronic properties.
Modulation of Olefin Metathesis Reactions by Chelation
Authors: Scherbakow Swetlana , Keller Manfred , Bannwarth Willi
Published: July 2014

We describe the modulation of catalytic activities by adjacent chelating entities as a new and hitherto unknown principle. It is demonstrated for ring‐closing metathesis (RCM) as well as for cross metathesis (CM) reactions. For this purpose, we have modified a Hoveyda‐type metathesis catalyst by employing two different chelators. Complexation of the chelators led to an electron‐withdrawing effect that resulted in enhanced catalytic activity. This enhancement was dependent on the complexed metal ion and allowed a gradual adjustment of the activity of the catalyst. The application of this new approach might be extendable to other catalytic systems as well.
Efficient One‐Pot Cross‐Coupling of Two Aryl Halides by Stannylation/Stille Reaction in Water under Microwave Irradiation
Authors: Tan Xin , Zhou Zi Jie , Zhang Jia Xin , Duan Xin Hong
Published: July 2014

A simple and highly efficient one‐pot approach has been developed for the Pd(PPh3)4‐catalyzed cross‐coupling of two different aryl or heteroaryl bromides/iodides. This method involves the combined use of microwave irradiation and water as a single solvent to achieve sequential stannylation and Stille cross‐coupling reactions, which allows rapid access to a wide variety of biaryls in good to high yields. Furthermore, utilizing this step‐economical protocol, 2,5‐dibromopyridine was iteratively diarylated and the Boscalid intermediate was also synthesized in a one‐pot manner.
Chemoselective Synthesis of N‐Protected Alkoxyprolines under Specific Solvation Conditions
Authors: Mihali Voichita , Foschi Francesca , Penso Michele , Pozzi Gianluca
Published: July 2014

N‐Protected hydroxyprolines (Hyp) were transformed chemoselectively into alkoxyproline derivatives by direct O‐alkylation. The starting Hyp was transformed into the corresponding dianion in a mixture of dimethyl sulfoxide and tetrahydrofuran (1:16 v/v) as solvent. Under these conditions, the carboxy‐anion showed reduced nucleophilicity because it was specifically solvated, and the more reactive oxy‐anion was selectively alkylated. N‐Protected trans‐4‐alkoxy‐, cis‐4‐alkoxy‐ and trans‐3‐alkoxyprolines were thus obtained in a single step in very high overall yields and with complete stability of the stereogenic center configuration.
Synthesis and Characterisation of 1,7‐Di‐ and Inherently Chiral 1,12‐Di‐ and 1,6,7,12‐Tetraarylperylenetetracarbox‐3,4:9,10‐diimides
Authors: Pagoaga Bernard , Giraudet Louis , Hoffmann Norbert
Published: July 2014

By using the Suzuki–Miyaura reaction, a variety of 1,7‐ and 1,12‐disubstituted and 1,6,7,12‐tetraaryl‐substituted perylenetetracarbox‐3,4:9,10‐diimides have been synthesised starting from the corresponding halogen derivatives. Until now, the 1,12‐ and 1,6,7,12‐sustitutions were difficult to access and only single examples have been reported. Dehydrohalogenation was observed to be competitive with the Suzuki–Miyaura reaction. The extent of this side reaction depends on the substitution pattern of the perylene diimide core and on the nature of the boronic acid derivative. Photochemical pericyclisation also reduces the yield of the desired products. A mechanistic analysis has been performed on the special case of 1,12‐diphenylperylenediimides, in which benzene is eliminated as a consecutive process of such a reaction. The energies of the frontier orbitals were determined. By using cyclic voltammetry, the energy of the LUMO was measured, and the energy gap between the frontier orbitals was determined based on optical spectroscopy (UV and fluorescence). With these two parameters, the energies of the HOMO were determined. The 1,6,7,12‐tetraaryl‐ and 1,12‐diarylperylenediimides have been optically resolved by using HPLC with a chiral stationary phase. Determination of absolute configuration was carried out by recording circular dichroism (CD) spectra of the enantiomers.
Cloudberry (Rubus chamaemorus) cell culture with bioactive substances: Establishment and mass propagation for industrial use
Authors: Nohynek Liisa , Bailey Michael , Tähtiharju Juha , Seppänen‐Laakso Tuulikki , Rischer Heiko , Oksman‐Caldentey Kirsi‐Marja , Puupponen‐Pimiä Riitta
Published: July 2014

The availability and quality of wild berry material is strongly affected by seasonal variations, human resources, and both chemical and biological pollutants. Here we describe for the first time the industrial scale biotechnological production of cloudberry (Rubus chamaemorus) cells of consistent quality and defined chemical composition. Callus was initiated from sterile cuts of the wild cloudberry leaves. Bright yellow, soft callus of uniform quality was selected by regular subculturing, and a stable line successfully used for suspension culture was obtained within 18 months. The cultivation process of the cell culture was initiated in 250 mL shake flasks and stepwise expanded to a stirred tank bioreactor of 300 L working volume. Each growth period in flasks and fed‐batch cultures in bioreactors was 10 ± 3 days. Viability of the cultures was approximately 90% throughout the cultivation processes. The 300 L culture was harvested by pressure filtration and the biomass was freeze‐dried. The 300 L yields of fresh cells and freeze‐dried material were 19 and 2 kg, respectively. The unusual phenolic profile of cloudberry cells including flavanols, as well as their fatty acid composition with a high proportion of α‐linolenic acid and high protein content, make them a unique and interesting alternative for industrial applications for various industrial fields.
The cytotoxic and genotoxic effects of metalaxy-M on earthworms (Eisenia fetida)
Authors: Liu Tong , Zhu Lusheng , Han Yingnan , Wang Jinhua , Wang Jun , Zhao Yan
Published: July 2014

As the main optical isomer of metalaxyl, metalaxyl-M has been widely used worldwide in recent years because of its notable effect on the prevention and control of crop diseases. Together with the toxicity and degradation of metalaxyl-M, the chemical has attracted the attention of researchers. The present study examined the toxic effects of metalaxyl-M on earthworms at 0 mg kg−1, 0.1 mg kg−1, 1 mg kg−1, and 3 mg kg−1 on days 7, 14, 21 and 28 after exposure. The results showed that metalaxyl-M could cause an obvious increase in the production of reactive oxygen species (ROS) when the concentration was higher than 0.1 mg kg−1, which led to lipid peroxidation in earthworms. Metalaxyl-M can induce DNA damage in earthworms, and the level of DNA damage markedly increased with increasing the concentration of metalaxyl-M. Metalaxyl-M also has a serious influence on the activities of antioxidant enzymes, which results in irreversible oxidative damage in cells. The changes of these indicators all indicated that metalaxyl-M may cause cytotoxic and genotoxic effects on earthworms. Environ Toxicol Chem 2014;33:2344–2350. © 2014 SETAC
A method for computing curved meshes via the linear elasticity analogy, application to fluid dynamics problems
Authors: Abgrall R. , Dobrzynski C. , Froehly A.
Published: July 2014

We propose and analyze an algorithm for the robust construction of curved meshes in two and three dimensions. The meshes are made of curved simplexes. The algorithm starts from a mesh made of straight simplexes, and using a linear elasticity analogy applied on well‐chosen data, one can generate a curved mesh. Note that if the initial mesh has a boundary layer, this method allows to conserve it on the final mesh. This algorithm is used on several airfoils in two and three dimensions, including a turbulent M6 wing. Copyright © 2014 John Wiley & Sons, Ltd.
Multicomponent intervention on enhancing dementia caregiver well‐being and reducing behavioral problems among Hong Kong Chinese: a translational study based on REACH II
Authors: Cheung Karen Siu‐Lan , Lau Bobo Hi‐Po , Wong Paul Wai‐Ching , Leung Angela Yee‐Man , Lou Vivian W. Q. , Chan Grace Man‐Yee , Schulz Richard
Published: July 2014

Objective

This study examined the effectiveness of a translated version of Resources for Enhancing Alzheimer's Caregiver Health (REACH) II in Hong Kong's service delivery context.

Method

The localized intervention was adapted from REACH II with 12 individual‐based sessions, which addressed multiple domains including disease education, safety, caregiver (CG) well‐being, and care recipients' problem behavior. Two‐hundred and one dementia family dyads completed the intervention.

Results

The efficacy of the intervention was demonstrated by the significant improvement in the perception of positive aspects of caregiving, reduction in depressive symptoms, subjective burden, bother and caregiving risks among CGs, and abatement in behavioral problems among care recipients. Treatment implementation was reflected from the high rate of adoption of each intervention component by interventionists and satisfactory reception from CGs. Promises in reach and adoption were demonstrated by the participation of 85 interventionists from 11 NGOs across 18 districts and CGs of a variety of demographic characteristics.

Discussion

This study is the first attempt to translate a highly successful evidence‐based dementia CG intervention developed in the USA into the Hong Kong service delivery context. The current results echoed the success of REACH II. The values and challenges of translational research are discussed. Copyright © 2014 John Wiley & Sons, Ltd.
Decreased limbic and increased fronto‐parietal connectivity in unmedicated patients with obsessive‐compulsive disorder
Authors: Göttlich Martin , Krämer Ulrike M. , Kordon Andreas , Hohagen Fritz , Zurowski Bartosz
Published: July 2014

Obsessive‐compulsive disorder (OCD) is characterized by recurrent intrusive thoughts and ritualized, repetitive behaviors, or mental acts. Convergent experimental evidence from neuroimaging and neuropsychological studies supports an orbitofronto‐striato‐thalamo‐cortical dysfunction in OCD. Moreover, an over excitability of the amygdala and over monitoring of thoughts and actions involving the anterior cingulate, frontal and parietal cortex has been proposed as aspects of pathophysiology in OCD. We chose a data driven, graph theoretical approach to investigate brain network organization in 17 unmedicated OCD patients and 19 controls using resting‐state fMRI. OCD patients showed a decreased connectivity of the limbic network to several other brain networks: the basal ganglia network, the default mode network, and the executive/attention network. The connectivity within the limbic network was also found to be decreased in OCD patients compared to healthy controls. Furthermore, we found a stronger connectivity of brain regions within the executive/attention network in OCD patients. This effect was positively correlated with disease severity. The decreased connectivity of limbic regions (amygdala, hippocampus) may be related to several neurocognitive deficits observed in OCD patients involving implicit learning, emotion processing and expectation, and processing of reward and punishment. Limbic disconnection from fronto‐parietal regions relevant for (re)‐appraisal may explain why intrusive thoughts become and/or remain threatening to patients but not to healthy subjects. Hyperconnectivity within the executive/attention network might be related to OCD symptoms such as excessive monitoring of thoughts and behavior as a dysfunctional strategy to cope with threat and uncertainty. Hum Brain Mapp 35:5617–5632, 2014. © 2014 Wiley Periodicals, Inc.
N,S,P‐Hybrid Donor–π–Acceptor Organic Dyes for Dye‐Sensitized Solar Cell: Synthesis, Optical Properties, and Photovoltaic Performances
Authors: Matano Yoshihiro , Hayashi Yukiko , Nakano Haruyuki , Imahori Hiroshi
Published: July 2014

New donor–π–acceptor organic (D–π–A) dyes composed of triarylamine, oligothiophene, and phosphole subunits were prepared, and their optical and photovoltaic properties were investigated. The regioselective α‐lithiation of the thiophene ring of 2‐(thiophen‐2‐yl)phospholes bearing an ester group, followed by treatment with tributyltin chloride afforded 2‐(5‐(tributylstannyl)thiophen‐2‐yl)phosphole derivatives, which underwent Stille coupling with 5′‐(p‐(diarylamino)phenyl)‐5‐bromo‐2,2′‐bithiophene to give triarylamine–terthiophene–phosphole hybrid π systems bearing the terminal ester group. The alkaline hydrolysis of the ester group yielded the target dyes, bearing the carboxylic acid anchoring group. The UV–vis absorption spectra of the new N,S,P‐hybrid dyes displayed broad and intense π–π* transitions with two absorption maxima in the visible region. Density functional theory (DFT) calculations of two dye models revealed that each highest occupied molecular orbital (HOMO) resides on the triarylamine–oligothiophene π network, whereas each lowest unoccupied molecular orbital (LUMO) is basically located on the phosphole subunit. In addition, the time‐dependent DFT calculations of the models showed that the lowest energy bands of these hybrid dyes are mainly consisted of the HOMO‐to‐LUMO+1 and HOMO‐to‐LUMO transitions with the large intramolecular charge‐transfer character. The N,S,P‐hybrid‐dye‐sensitized TiO2 cells exhibited moderate power conversion efficiencies of up to 5.6%. The present findings corroborate the potential utility of the phosphole skeletons as the acceptor components in the D–π–A sensitizers.