bluuebunny/crossref_metadata_2025_split huggingface dataset:
Simulated climate change conditions unveil the toxic potential of the fungicide pyrimethanil on the midge Chironomus riparius: a multigeneration experiment
Authors: Müller Ruth , Seeland Anne , Jagodzinski Lucas S. , Diogo Joao B. , Nowak Carsten , Oehlmann Jörg 
Published: December 2011

AbstractAlthough it has been suggested that temperature increase may alter the toxic potential of environmental pollutants, few studies have investigated the potential risk of chemical stressors for wildlife under Global Climate Change (GCC) impact. We applied a bifactorial multigeneration study in order to test if GCC conditions alter the effects of low pesticide concentrations on life history and genetic diversity of the aquatic model organism Chironomus riparius. Experimental populations of the species were chronically exposed to a low concentration of the fungicide pyrimethanil (half of the no‐observed‐adverse‐effect concentration: NOAEC/2) under two dynamic present‐day temperature simulations (11.0–22.7°C; 14.0–25.2°C) and one future scenario (16.5–28.1°C). During the 140‐day multigeneration study, survival, emergence, reproduction, population growth, and genetic diversity of C. riparius were analyzed. Our results reveal that high temperature and pyrimethanil act synergistically on the midge C. riparius. In simulated present‐day scenarios, a NOAEC/2 of pyrimethanil as derived from a life‐cycle toxicity test provoked only slight‐to‐moderate beneficial or adverse effects on C. riparius. In contrast, exposure to a NOAEC/2 concentration of pyrimethanil at a thermal situation likely for a summer under GCC conditions uncovered adverse effects on mortality and population growth rate. In addition, genetic diversity was considerably reduced by pyrimethanil in the future scenario, but only slightly under current climatic conditions. Our multigeneration study under near‐natural (climatic) conditions indicates that not only the impact of climate change, but also low concentrations of pesticides may pose a reasonable risk for aquatic insects in future.
Platinum(II) Complexes Bearing a Thiolate/Thioether Ligand – Hemilability vs. Dealkylation
Authors: Guyon Fabrice , Knorr Michael , Garillon Aurélie , Strohmann Carsten 
Published: December 2011

AbstractSubstitution of the chloro ligands of cis‐[Pt(PEt3)2Cl2] by 4‐methylthio‐2‐thioxo‐1,3‐dithiole‐5‐thiolate (L) leads to the thiolato complexes trans‐[Pt(PEt3)2ClL] (2) and trans‐[Pt(PEt3)2L2] (1), which have been characterised by X‐ray crystallography. In the solid state, the square planar arrangement is capped by an endocyclic sulfur atom of L, which gives rise to distorted square‐pyramidal and pseudooctahedral geometries for 2 and 1, respectively. Complex 1 coexists in solution with [Pt(PEt3)(η1‐L)(η2‐L)] (3), which results from the reversible dissociation of one phosphane ligand. The combination of η1‐(thiolato) and η2‐(thiolato/thioether) L in 3 has been established by variable‐temperature 1H NMR spectroscopy and crystal structure determination. The η2‐coordination mode of L is also observed in cis‐[Pt(PEt3)2L]+ (4), which results from the abstraction of the chloro ligand of 2 by excess TlPF6. An S‐demethylation reaction occurs when 1 is heated in acetonitrile to yield the structurally‐characterised dithiolene complex [Pt(PEt3)2(dmit)] (5) (dmit2– = 2‐thioxo‐1,3‐dithiole‐4,5‐dithiolate) and MeL. Treatment of cis‐[Pt(PPh3)2Cl2] with 2 equiv. of L leads to a mixture of [Pt(PPh3)2(dmit)] (6) and [Pt(PPh3)(η1‐L)(η2‐L)] (7). Complex 7 predominates in solution over its parent compound,[Pt(PPh3)2L2]. The identification of CH3Cl by 1H NMR spectroscopy proves that [Pt(PPh3)2ClL] is involved as an intermediate in the demethylation process. The reaction of L with platinum precursors that are blocked in a cis arrangement by chelation of 1,1‐bis(diphenylphosphanyl)methane (dppm) and 1,1‐bis(diphenylphosphanyl)ethane (dppe) leads to the formation of the thiolato complexes cis‐[Pt(η2‐dppm)L2] (8) and cis‐[Pt(η2‐dppe)L2] (9). The solid‐state structure of 8 reveals the occurrence of an additional weak interaction between a thiomethyl group and the platinum centre (Pt–S 3.073 Å).
Well‐Defined Heterometallic and Unsymmetric M2O2 Complexes Arising from Binding and Activation of O2
Authors: Garcia‐Bosch Isaac , Ribas Xavi , Costas Miquel 
Published: December 2011

AbstractOxygen binding and activation reactions at dimetal sites constitute chemical processes of fundamental interest, because of the implication of these reactions in biology, chemical synthesis, and catalysis. This account collects and discusses studies of O2 binding and/or activation by inequivalent dimetal sites, and it specially focuses on systems in which O2‐bound reaction intermediates have been experimentally characterized. Homometallic unsymmetric systems and heterometallic complexes are reviewed, and their chemistry in oxidative transformations is described. Introduction of asymmetry into M2O2 cores poses important challenges to their preparation, and strategies developed to address this problem are discussed. Distinct spectroscopic and chemical properties emerge from these unsymmetric systems.
Atomic Layer Deposition of Titanium and Vanadium Oxide on Mesoporous Silica and Phenol/Formaldehyde Resins – the Effect of the Support on the Liquid Phase Epoxidation of Cyclohexene
Authors: Muylaert Ilke , Musschoot Jan , Leus Karen , Dendooven Jolien , Detavernier Christophe , Van Der Voort Pascal 
Published: December 2011

AbstractTitanium and vanadium oxide layers have been grown in the pores of two 2D hexagonal ordered mesoporous materials: SBA‐15 (silica) and FDU‐15 (phenol/formaldehyde resin). The deposition of the layers was controlled by the self‐limiting reaction of the metal oxide precursor with the hydroxyl surface. Single, multiple and mixed titanium and vanadium oxide layers have been synthesised, and the influence of the layer type on the catalytic performance in the liquid phase epoxidation of cyclohexene has been evaluated. The effect of the support on the catalytic behaviour is discussed, and a reaction mechanism is proposed. The support–oxygen–metal bond is assumed to be critical for catalytic epoxidation.
Carica papaya latex: A low‐cost biocatalyst for human milk fat substitutes production
Authors: Tecelão Carla , Rivera Ivanna , Sandoval Georgina , Ferreira‐Dias Suzana 
Published: December 2011

AbstractThis work aims at evaluating the potential of Carica papaya lipase (CPL) self‐immobilized in papaya latex as a biocatalyst for the synthesis of human milk fat substitutes (HMFS), to be used as a low‐cost alternative to commercial lipases. Two different CPL preparations, one extracted from the papaya fruit (CPL I) and the other from petiole leaves (CPL II) of papaya tree, were tested as catalysts for the acidolysis between tripalmitin and (i) oleic acid or (ii) omega‐3 PUFA, batchwise, at 60°C, in solvent‐free media. After 24 h, molar incorporation was higher for oleic acid (22.1 mol%) when CPL I was used. This biocatalyst was selected for further studies. RSM was used to model reaction conditions: medium formulation (molar ratio oleic acid/tripalmitin, MR, 1.2:1–6.8:1) and temperature (58–72°C). Acyl migration decreased with MR increase. In batch operational stability assays at 60°C, using MR of 2:1 and 6:1, the highest stability was observed for a MR of 2:1.Practical applications: The use of this biocatalyst is a feasible way to valorize papaya agro‐residues which represent an important environmental problem in the producing countries. The obtained results were rather promising since, with this almost zero‐cost biocatalyst, it was possible to produce a high added‐value product (HMFS). Under optimized conditions, the obtained results were comparable with those obtained with expensive immobilized commercial lipases.
Lipidomic profiling and discovery of lipid biomarkers in snow alga Chlamydomonas nivalis under salt stress
Authors: Lu Na , Wei Dong , Chen Feng , Yang Shang‐Tian 
Published: December 2011

AbstractThe snow alga Chlamydomonas nivalis is a typical microalgal species that can adapt and resist to natural habitats in the polar region and similar extreme environments. In response to various stress conditions, the change of lipid profile in cell membrane systems is known to play a vital role in cell survival and reproduction. In the present work, to elucidate the involvement of intracellular lipids in the molecular mechanism of cell response and adaptation to salt stress, C. nivalis was cultured and treated with different sodium chloride (NaCl) concentrations in different time courses. The ultra performance liquid chromatography/quadrupole‐TOF‐MS (UPLC/Q‐TOF‐MS)‐based approach was developed for lipidomic profiling followed by multivariate statistical analysis including partial least squares discriminant analysis and orthogonal projection on latent structure discriminant analysis for data classification and potential biomarkers selection. Seven types and 35 kinds of polar lipid molecules were selected and identified as biomarkers, including monogalactosyldiacylglycerol, digalactosyldiacylglycerol, l, 2‐diacylglyceryl‐3‐O‐4′‐(N,N,N‐trimethyl)‐homoserine, phosphatidylglycerol, sulfoquinovosyl‐diacylglycerol, phosphatidylethanolamine, and phosphatidylinositiol. Their functions in relation to the regulation of cell membrane stability, signal transduction and photosynthesis efficiency under salt stress are also discussed in this paper. This is the first study using UPLC/Q‐TOF‐MS‐based lipidomic profiling with multivariate statistical analysis for lipid biomarkers discovery from microalgae in response to stress conditions.
Synthesis and Characterization of Adducts Formed in the Reactions of Safrole 2′,3′‐Oxide with 2′‐Deoxyadenosine, Adenine, and Calf Thymus DNA
Authors: Shen Li‐Ching , Chiang Su‐Yin , Ho I‐Ting , Wu Kuen‐Yuh , Chung Wen‐Sheng 
Published: December 2011

AbstractSafrole (1) is a natural product found in herbs and spices. Upon uptake, it can be metabolized to safrole 2′,3′‐oxide [(±)‐SFO, 2], which can react with DNA bases to form DNA adducts. The reactions of 2 with 2′‐deoxyadenosine (3) and adenine (8) under physiological conditions (pH 7.4, 37 °C) were carried out to characterize its possible adducts with adenine. Four adducts were isolated by reverse‐phase liquid chromatography and their structures were characterized by UV/Vis, 1H and 13C NMR spectroscopy and MS. The reaction of 2 with 3 produced two regioisomers, N1γ‐SFO‐dAdo (4) and N6γ‐SFO‐dAdo (5), in 4.2–4.5 % yield, and the reaction of 2 with 8 generated N3γ‐SFO‐Ade (9) and N9γ‐SFO‐Ade (10) in 1.0–2.4 % yield. Using HPLC–ESI‐MS/MS, we traced the amounts of the four adducts formed when calf thymus DNA (10 mg) was treated with 2 (60 μmol) and the levels of 4, 5, and 9 were determined to be 2000, 170, and 660 adducts per 106 nucleotides, respectively. Adduct 10 was not detected under these conditions. These results suggested that stable DNA adducts of 2 were formed in vitro, and further studies on the formation of these DNA adducts in vivo may help to elucidate their role in safrole carcinogenicity.
Palladium‐Catalyzed Selective Synthesis of Naphthalenes and Indenones and Their Luminescent Properties
Authors: Chen Xiaopeng , Jin Jisong , Wang Ningning , Lu Ping , Wang Yanguang 
Published: December 2011

AbstractSelective synthesis of functionalized naphthalenes and indenones by palladium‐catalyzed cyclization of o‐haloacetophenones and terminal alkynes in the presence of a secondary amine is reported. Under a nitrogen atmosphere, the palladium‐catalyzed reaction of o‐haloacetophenones with terminal alkynes in the presence of wet secondary aminesgenerated 1‐(dialkylamino)‐3‐aryl/alkylnaphthalenes. When the reaction was conducted in air, 1‐indenone‐3‐carbaldehydes were obtained. The synthesized β‐arylnaphthalenes 4a–f emit light in a range from 386 to 452 nm with quantum yields from 0.10 to 0.48 in cyclohexane. The absorption and emission efficiency of 4d were finely tuned by the acidity of the environment, and this might be useful in the use of 4d as a fluorescent pH sensor.
Total Synthesis of Indolizidine (+)‐223A
Authors: Fellah Mouloud , Lhommet Gérard , Mouriès‐Mansuy Virginie 
Published: December 2011

AbstractWe described the diastereoselective total synthesis of indolizidine (+)‐223A in 10 % overall yield over 14 steps starting from 6‐chlorohex‐2‐ynoate. Our strategy involved chain elongation through aldolization, the formation of the indolizidine skeleton by cyclization, and stereocontrolled hydrogenation.
One‐Pot Synthesis of 3,4‐Disubstituted Coumarins under Catalysis of Mn3O4 Nanoparticles
Authors: Sun Huayin , Zhang Yonghui , Guo Fengfeng , Yan Yizhe , Wan Changfeng , Zha Zhenggen , Wang Zhiyong 
Published: December 2011

AbstractThe one‐pot synthesis of 3,4‐disubstituted coumarins from substituted 2‐(hydroxymethyl)phenols with β‐keto esters catalyzed by Mn3O4 nanoparticles was developed. A series of 3,4‐disubstituted coumarin derivatives were obtained in good yields.
Communication between Components in Metal‐Directed Assemblies of Oriented Calix[6]arene‐Based Pseudorotaxanes and Rotaxanes
Authors: Arduini Arturo , Bussolati Rocco , Masseroni Daniele , Royal Guy , Secchi Andrea 
Published: December 2011

AbstractOriented calix[6]arene‐based pseudorotaxanes and rotaxanes where the axial component bears a terpyridine ligand as a stopper positioned at the upper rim of the calixarene have been synthesized. The binding ability of the terpyridine unit present in the axle toward zinc salts is affected by the presence of the wheel, its distance with respect to the calix[6]arene upper rim, and the nature of the counterion of the zinc salt employed. Metal coordination at the terpyridine unit changes the electrochemical behavior of the 4,4′‐bipyridinium unit of the axle inside the wheel in both the pseudorotaxanes and rotaxanes.
Organic monoliths for hydrophilic interaction electrochromatography/chromatography and immunoaffinity chromatography
Authors: Gunasena Dilani N. , El Rassi Ziad 
Published: December 2011

AbstractThis article is aimed at providing a review of the progress made over the past decade in the preparation of polar monoliths for hydrophilic interaction LC (HILIC)/capillary electrochromatography (HI‐CEC) and in the design of immuno‐monoliths for immunoaffinity chromatography that are based on some of the polar monolith precursors used in HILIC/HI‐CEC. In addition, this review article discusses some of the applications of polar monoliths by HILIC and HI‐CEC, and the applications of immuno‐monoliths. This article is by no means an exhaustive review of the literature; it is rather a survey of the recent progress made in the field with 83 references published in the past decade on the topics of HILIC and immunoaffinity chromatography monoliths.
Using the gene ontology to scan multilevel gene sets for associations in genome wide association studies
Authors: Schaid Daniel J. , Sinnwell Jason P. , Jenkins Gregory D. , McDonnell Shannon K. , Ingle James N. , Kubo Michiaki , Goss Paul E. , Costantino Joseph P. , Wickerham D. Lawrence , Weinshilboum Richard M. 
Published: December 2011

AbstractGene‐set analyses have been widely used in gene expression studies, and some of the developed methods have been extended to genome wide association studies (GWAS). Yet, complications due to linkage disequilibrium (LD) among single nucleotide polymorphisms (SNPs), and variable numbers of SNPs per gene and genes per gene‐set, have plagued current approaches, often leading to ad hoc “fixes.” To overcome some of the current limitations, we developed a general approach to scan GWAS SNP data for both gene‐level and gene‐set analyses, building on score statistics for generalized linear models, and taking advantage of the directed acyclic graph structure of the gene ontology when creating gene‐sets. However, other types of gene‐set structures can be used, such as the popular Kyoto Encyclopedia of Genes and Genomes (KEGG). Our approach combines SNPs into genes, and genes into gene‐sets, but assures that positive and negative effects of genes on a trait do not cancel. To control for multiple testing of many gene‐sets, we use an efficient computational strategy that accounts for LD and provides accurate step‐down adjusted P‐values for each gene‐set. Application of our methods to two different GWAS provide guidance on the potential strengths and weaknesses of our proposed gene‐set analyses.
Lifetime romantic attachment style and social adaptation in late‐onset depression
Authors: Paradiso Sergio , Naridze Rachelle , Holm‐Brown Erika 
Published: December 2011

BackgroundMeasuring social adjustment (including attachment style and current social adaptation) in late‐life depression may support planning secondary prevention, rehabilitation, and treatment. Insecure attachment style is a risk factor for developing new depression, and social adjustment may constitute a problem after symptoms abatement. Few studies have examined attachment style and social adjustment in late‐onset depression.DesignSubjects 50 years of age and older with early‐onset (n = 35), late‐onset DSM‐IV unipolar depression (n = 38), and never‐depressed volunteers (n = 47) were assessed with a widely used measure of attachment style (the Experiences in Close Relationship Scale). Social adjustment was measured using the Social Adjustment Scale.ResultsBoth early‐onset and late‐onset patients with depression showed greater insecure attachment and poorer social adaptation compared with never‐depressed volunteers. No difference was found between early‐onset and late‐onset patients with depression on attachment style or social adjustment. There were no significant differences between late‐life depression in remission or current on attachment or social adaptation.ConclusionInsecure attachment style may be a risk factor for late‐life depression irrespective of the age of onset. Social maladaptation may persist among individuals with late‐life depression in remission. Copyright © 2011 John Wiley & Sons, Ltd.
Secreted amyloid precursor proteins promote proliferation and glial differentiation of adult hippocampal neural progenitor cells
Authors: Baratchi Sara , Evans Jane , Tate Warren P. , Abraham Wickliffe C. , Connor Bronwen 
Published: December 2011

AbstractAmyloid precursor protein (APP) is an integral membrane glycoprotein present at high levels in nerve cells. Two soluble secreted forms, sAPPα and sAPPβ, are processed from APP by two mutually exclusive proteolytic pathways. sAPPα shows a range of neuroprotective and growth factor properties, including reduction of neuronal injury and improvement in memory performance, in contrast to the generally less potent sAPPβ. In addition, sAPPα has been shown to increase the proliferation of both embryonic neural stem cells and neural progenitor cells (NPCs) derived from the subventricular zone (SVZ) of the adult brain. However, an effect of sAPPα (or sAPPβ) on adult hippocampal progenitor cell proliferation and differentiation has not previously been observed. In this study, we examined the effect of both the α‐ and β‐cleaved ectodomains of sAPP on adult NPCs isolated from the subgranular zone (SGZ) of the rat hippocampus in the presence or absence of depolarizing conditions. Assays were performed to examine the effect of sAPPα and sAPPβ on SGZ‐derived adult NPC proliferation in parallel with SVZ‐derived cells and on differentiation with SGZ‐derived cells. We observed both sAPPα and sAPPβ increased the proliferation of SGZ‐derived NPCs in vitro. Further, treatment of SGZ‐derived NPCs with either sAPPα or sAPPβ increased the number of cells expressing the astrocytic marker GFAP and promoted cell survival. The effect on differential fate was observed in both the presence and absence of depolarizing conditions. Thus, both sAPPα and sAPPβ exert a complex range of effects on SGZ‐derived adult NPCs, including increasing NPC proliferation, maintaining cell viability, yet promoting glial over neuronal differentiation. These findings provide the first direct support for the secreted forms of APP regulating SGZ‐derived NPCs, and raise the possibility some or all of the effects may have therapeutic benefit in models of neurological disease. © 2011 Wiley Periodicals, Inc.
BENCHMARKING FOR WATER USERS ASSOCIATIONS TO ENHANCE PERFORMANCE OF THE SAMRAT ASHOK SAGAR MAJOR IRRIGATION SCHEME
Authors: Phadnis Sanjay Sitaram , Kulshrestha Mukul 
Published: December 2011

ABSTRACTWater is one of the most scarcely available natural resource on earth. Its effective utilisation is a major concern felt worldwide. Water crisis is a situation felt in every sector using it (domestic, power, industry and irrigation). Exploitation of water resources in an unplanned manner has resulted in deterioration of environmental and social conditions and has resulted in an alarming situation. The Samrat Ashok Sagar Major Irrigation Scheme of the Madhya Pradesh Water Resources Department, India, was selected as a study area for the benchmarking of irrigation performance assessment by the Water Users Associations for the years 2003–2004 to 2007–2008. The Indian National Committee for Irrigation and Drainage (ICID) and the Water Resources Department, Maharashtra, India, recommended selected indicators for benchmarking of the irrigation and drainage sector. The objective of this study was to implement internal benchmarking to improve the performance of the system by creating competition between water users associations working in a major irrigation scheme. Copyright © 2011 John Wiley & Sons, Ltd.
Homology of the internal sac components in the leaf beetle subfamily criocerinae and evolutionary novelties related to the extremely elongated flagellum
Authors: Matsumura Yoko , Yoshizawa Kazunori 
Published: December 2011

AbstractExtremely elongated intromittent organs are found in a wide range of taxa, especially among insects. This phenomenon is generally thought to result from sexual selection, but it is predicted that limited storage space in the body cavity and the difficulty of using the elongated organs should have constrained the evolution of extreme elongation, neutralizing any selective advantage. Therefore, in groups with long intromittent organs, features that overcome these constraints may have evolved or coevolved together with intromittent organ elongation. Using a comparative morphological approach and outgroup comparisons, we identified potential constraints and key novelties that may neutralize such constraints in the leaf beetle subfamily Criocerinae. Observations of the internal sac structure throughout Criocerinae were performed. Comparing the results with preceding studies from outgroups, a ground plan of the criocerine internal sac was constructed. Our analysis also identified specific features that are always correlated with extreme elongation: the rotation of whole internal‐sac sclerites and the possession of a pocket in which to store the elongated flagellum. The pocket is thought to be formed by the rotation of the sclerites, markedly altering internal sac shape from the criocerine ground plan. Onlythe clades that have acquired this derived state contain species with an elongated flagellum that distinctly exceeds the median lobe length. It is presumed that these character correlations evolved independently three times. The detected character correlations corroborate the hypothesis that there are latent adaptive constraints for the evolution of extremely elongated intromittent organs. The constraints may have been neutralized by the alteration from the criocerine ground plan resulting in the formation of a storage pocket. In conclusion, deviation from the criocerine ground plan isconsidered to be the evolutionary innovation that neutralized the latent adaptive constraints of flagellum elongation in the subfamily Criocerinae. J. Morphol., 2012. © 2011 Wiley Periodicals, Inc.