bluuebunny/crossref_metadata_2025_split huggingface dataset:
Periphery‐Hydrogenating Effects on the Unordinary 14 π‐Electron Delocalized Circuits and Related Electronic Properties of Subporphyrazine Analogs: A Density Functional Theory Investigation
Authors: Zhao Luyang , Qi Dongdong , Cai Xue , Jiang Jianzhuang 
Published: September 2012

AbstractDensity functional theory method was employed to investigate the electronic properties of two series of subporphyrazine and subphthalocyanine derivatives, namely SubPz, SubPz‐1H, SubPz‐2H, SubPz‐3H, SubPc, SubPc‐1H, SubPc‐2H, and SubPc‐3H. Calculated results show that peripheral hydrogenation essentially changes the delocalized pattern from the common π1414 to limited π1314 or π1214 for SubPz series, and substantially weakens the aromaticity for both SubPz and SubPc compounds. The unordinary delocalized circuit owns an unstable energy level, and thus gives rise to a notable transformation of geometric configuration, frontier molecular orbital topology, and absorption spectral bands.
Halloysite Nanotubes, a Multifunctional Nanovehicle for Anticancer Drug Delivery
Authors: Guo Mingyi , Wang Aifei , Muhammad Faheem , Qi Wenxiu , Ren Hao , Guo Yingjie , Zhu Guangshan 
Published: September 2012

AbstractTargeted drug delivery systems have attracted a great deal of interest by virtue of their potential use in chemotherapy. In this study, multicomponent halloysite nanotubes (HNTs) have been evaluated as a platform to assist and direct the delivery of anticancer drug doxorubicin (DOX) into cancer cells. Folic acid (FA) and magnetite nanoparticles were successfully grafted onto HNTs via amide reaction whereas the drug has been introduced by capitalizing electrostatic interaction between cationic drug and anionic exterior of HNTs, which eventually leads to pH responsive release. The resultant DOX loaded FA‐Fe3O4@HNTs were well characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and XRD. The clinical efficacy of the system was validated by confocal microscopy and cell cytotoxicity assay (MTT assay). MTT assay results revealed a high biocompatibility up to a concentration of 200 µg/mL of HNTs, while, DOX loaded FA‐Fe3O4@HNTs were markedly cytotoxic to HeLa cells. This multifunctional nanovehicle has a great potential for cancer diagnosis and therapy, and could further advance the clinical use of nanomedicine.
Palladium‐Catalyzed Synthesis of Aromatic Sultones via Sulfonic Acid Group‐Directed CH Activation
Authors: Li Fei , Jiang Taoshan , Cai Haiting , Wang Guanwu 
Published: September 2012

AbstractAromatic sultones could be obtained by the palladium‐catalyzed cyclization reaction of arylsulfonic acids with simple arenes. The reaction proceeds through sulfonic acid group‐directed multiple CH activations and involves the cleavage of CH and OH bonds as well as the formation of CC and CO bonds. Our protocol provides a facile access to aromatic sultones.
Dehydration of Carbohydrates to 5‐Hydroxymethylfurfural in Ionic Liquids Catalyzed by Hexachlorotriphosphazene
Authors: Song Jinliang , Zhang Binbin , Shi Jinghua , Ma Jun , Yang Guanying , Han Buxing 
Published: September 2012

AbstractDevelopment of efficient catalysts for the dehydration of carbohydrates to produce 5‐hydroxymethylfurfural (HMF) is a very attractive topic. In this work, dehydration of fructose catalyzed by three organic molecules, including hexachlorotriphosphazene (N3P3Cl6), trichloromelamine (C3N6H3Cl3) and N‐bromosuccinimide (NBS), was studied in ionic liquids. It was discovered that the three organic molecules had high activity in accelerating the dehydration of fructose and N3P3Cl6 was the most efficient catalyst among them. The effects of amount of catalysts, temperature, solvents, reaction time, and substrate/solvent weight ratio on the reaction were investigated using N3P3Cl6 as the catalyst and 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl) as the solvent. It was demonstrated that the N3P3Cl6/[Bmim]Cl catalytic system was very effective for catalyzing the reaction. The yield of HMF could reach 92.8% in 20 min at the optimized conditions and the N3P3Cl6/[Bmim]Cl system could be reused. Further study indicated that the N3P3Cl6/[Bmim]Cl system was also effective for the dehydration of sucrose and inulin and satisfactory yield could be obtained at suitable conditions.
Enantioselective Synthesis of Terminal 1,2‐Diols from Acyl Chlorides
Authors: Shao Panlin , Shen Litao , Ye Song 
Published: September 2012

AbstractOptically active terminal 1,2‐diols were prepared with high enantiopurity via the TMS‐quinidine‐catalyzed enantioselective cyclization of acyl chlorides and oxaziridine, followed by reductive ring‐opening of the cycloadducts.
Open Tubular Microreactor with Enzyme Functionalized Microfluidic Channel for Amperometric Detection of Glucose
Authors: Zhang Lei , Qu Ping , Sheng Jin , Lei Jianping , Ju Huangxian 
Published: September 2012

AbstractA simple and efficient method using enzyme immobilized microfluidic channel as open tubular microreactor was designed for amperometric detection of glucose. The microreactor was composed of a polydimethylsilicone/glass hybrid device with three reservoirs, a cooling cave and a 6 cm capillary with a sampling fracture as microchannel. The microchannel was further modified by thermal polymerization, followed by covalently attaching with glucose oxidase. Through fracture sampling and electrochromatography separation, the production via enzymatic reaction was determinated by Pt electrode at the end of capillary. The linear range for the detection of glucose was 0.05–7.5 mmol·L−1 with detection limit of 23 µmol·L−1. The inter‐ and intra‐chip reproducibilities for determination of 2.5 mmol·L−1 glucose were 98.5% (n=5) and 96.0% (n=5), respectively. With the advantage of flexible assembly, rapid efficiency, good stability and low‐cost, this microreactor provided a potential platform for establishing a portable enzyme‐based chemical detection system in practical application.
Enantioselective Morita‐Baylis‐Hillman Reaction Organocatalyzed by Glucose‐based Phosphinothiourea
Authors: Yang Weihong , Sha Feng , Zhang Xin , Yuan Kui , Wu Xinyan 
Published: September 2012

AbstractA class of bifunctional phosphinothioureas derived from saccharide was developed as new organocatalysts for the enantioselective Morita‐Baylis‐Hillman reaction between acrylates and aldehydes. With 10 mol% of glucose‐based phosphinothiourea 1d, the allylic alcohols were obtained in up to 96% yield and 83% ee under mild reaction conditions.
One‐Pot Synthesis of Pyrrolo[1,2‐a]indoles by Chiral N‐Triflyl Phosphoramide Catalyzed Friedel‐Crafts Alkylation of 4,7‐Dihydroindole with β,γ‐Unsaturated α‐Keto Esters
Authors: Zeng Mi , Zhang Wei , You Shuli 
Published: September 2012

AbstractChiral N‐triflyl phosphoramide was found an efficient catalyst for the enantioselective Friedel‐Crafts alkylation reaction of 4,7‐dihydroindole with β,γ‐unsaturated α‐keto esters. In the presence of 5 mol% of the optimized catalyst, various pyrrolo[1,2‐a]indoles were obtained in excellent enantioselectivity, moderate yields and up to 3:1 diastereoselectivity based on the one‐pot synthesis including the Friedel‐Crafts alkylation reaction and the subsequent p‐benzoquinone oxidation.
Equivariant Characteristic Classes of Singular Complex Algebraic Varieties
Authors: Cappell Sylvain E. , Maxim Laurentiu G. , Schürmann Jörg , Shaneson Julius L. 
Published: September 2012

AbstractHomology Hirzebruch characteristic classes for singular varieties have been recently defined by Brasselet, Schüurmann, and Yokura as an attempt to unify previously known characteristic class theories for singular spaces (e.g., MacPherson‐Chern classes, Baum‐Fulton‐MacPherson Todd classes, and Goresky‐MacPherson $L$‐classes). In this paper we define equivariant analogues of these classes for singular quasi‐projective varieties acted upon by a finite group of algebraic automorphisms and show how these can be used to calculate the homology Hirzebruch classes of global quotient varieties. We also compute the new classes in the context of monodromy problems, e.g., for varieties that fiber equivariantly (in the complex topology) over a connected algebraic manifold. As another application, we discuss Atiyah‐Meyer type formulae for twisted Hirzebruch classes of global orbifolds. © 2012 Wiley Periodicals, Inc.
Rare Event Simulation of Small Noise Diffusions
Authors: Vanden‐Eijnden Eric , Weare Jonathan 
Published: September 2012

AbstractAn important sampling method for certain rare event problems involving small noise diffusions is proposed. Standard Monte Carlo schemes for these problems behave exponentially poorly in the small noise limit. Previous work in rare event simulation has focused on developing estimators with optimal exponential variance decay rates. This criterion still allows for exponential growth of the statistical relative error. We show that an estimator related to a deterministic control problem not only has an optimal variance decay rate but can have vanishingly small relative statistical error in the small noise limit. The sampling method based on this estimator can be seen as the limit of the zero variance importance sampling scheme, which uses the solution of the second‐order partial differential equation (PDE) associated with the diffusion. In the scheme proposed here this PDE is replaced by a Hamilton‐Jacobi equation whose solution is computed pointwise on the fly from its variational formulation, an operation that remains practical even in high‐dimensional problems. We test the scheme on several simple illustrative examples as well as a stochastic PDE, the noisy Allen‐Cahn equation. © 2012 Wiley Periodicals, Inc.
Inability of a monoclonal anti‐light chain antibody to detect clonal plasma cells in a patient with multiple myeloma by multicolor flow cytometry
Authors: van Velzen Jeroen F. , van den Blink Dorine , Bloem Andries C. 
Published: September 2012

AbstractBackground:Multicolor flow cytometry (MFC) is increasingly important for the diagnosis and minimal residual disease (MRD) assessment of patients with plasma cells (PC) dyscrasias, like multiple myeloma. Recently published information shows that immunophenotype of myeloma PC can change over time and normal PC are heterogeneous in the expression of CD19 and CD56. This implies that for a sensitive, reliable detection of MRD clonality assessment by the detection of cytoplasmic kappa and lambda light chains is advisable.Methods:Eight‐color MFC was used to detect normal and myeloma PC by the expression of CD38 and CD138. Analysis of additional surface antigens like CD45, CD19, CD56, CD27, and the intracellular immunoglobulin light chain distribution were used to differentiate polyclonal from clonal PC.Results:Absence of cytoplasmic light chains expression in a PC subpopulation with an abnormal phenotype suggested the presence of non‐secretory plasma cells in the bone marrow (BM) of this patient. This observation however, was contradicted by the presence of free lambda light chains in the patient's serum. After repeating the analysis with polyclonal antibodies against intracellular immunoglobulin light chains instead of monoclonal antibodies, the abnormal PC subpopulation appeared to express lambda light chains.Conclusion:These data illustrate that if clonality assessment of PC is included in disease monitoring, the use of polyclonal over monoclonal antibodies is preferred for the detection of intracellular immunoglobulin light chains. © 2012 International Clinical Cytometry Society
Feeding disorders of early childhood: An empirical study of diagnostic subtypes
Authors: Lucarelli Loredana , Cimino Silvia , D'Olimpio Francesca , Ammaniti Massimo 
Published: September 2012

AbstractObjective:The aim of this study was to examine the differences among three subtypes of feeding disorders (FD), defined through the criteria of the DC:0‐3R: “Infantile Anorexia” (IA), “Feeding Disorder Associated with Insults to the Gastrointestinal Tract” (FDIGT), and “Sensory Food Aversions” (SFA), by exploring mother–child interactions during feeding, children's temperament and emotional–adaptive functioning, and mothers' psychological profile and eating attitudes.Method:The sample consisted of 146 Italian mother–child pairs, of which 51 children with IA, 47 children with FDIGT, and 48 mothers and their children with SFA. All dyads were videotaped during feeding; mothers completed questionnaires assessing their psychological profiles and eating attitudes, as well as their children's temperament and emotional/behavioral functioning.Results:Analyses revealed significant differences between the diagnostic groups of FD in relation to mother–child interactions during feeding, children's temperament and emotional–adaptive functioning, and mothers' psychological profile and eating attitudes.Discussion:Both interactional and individual variables may contribute differently to specific FD and outcomes during childhood. Definitions by FD subtypes, using operational diagnostic criteria, and the assessment of mother–child interactions are relevant to target interventions strategies to treat specific disorders. © 2012 by Wiley Periodicals, Inc. (Int J Eat Disord 2013)
Genetic structure along an altitudinal gradient in Lippia origanoides, a promising aromatic plant species restricted to semiarid areas in northern South America
Authors: Vega‐Vela Nelson Enrique , Sánchez María Isabel Chacón 
Published: September 2012

AbstractThe genetic diversity and population structure of Lippia origanoides, a species of the Verbenaceae family that shows promise as a crop plant, was investigated along an altitudinal gradient in the basin of the Chicamocha River in northeastern Colombia. The economic importance of the species, quality of its essential oils, and the fact that it is restricted to some few semiarid areas in northern South America may put the species at risk in a scenario of uncontrolled harvest of natural populations. Lippia origanoides was sampled along an altitudinal gradient from 365 to 2595 m.a.s.l. throughout Chicamocha River Canyon, a semiarid area in northeastern Colombia. Genetic diversity was assessed by means of AFLP markers. The number of AFLP loci (355) and the number of individuals sampled (173) were sufficient to reliably identify four populations at contrasting altitudes (FST = 0.18, P‐value < 0.0000), two populations in the lower basin, one population in the medium basin, and one population in the upper basin, with a low level of admixture between them. In average, genetic diversity within populations was relatively high (Ht = 0.32; I = 0.48); nevertheless, diversity was significantly reduced at higher altitude, a pattern that may be consistent with a scenario of range expansion toward higher elevations in an environment with more extreme conditions. The differences in altitude among the basins in the Chicamocha River seem to be relevant in determining the genetic structure of this species.
The Mechanical Performance of a Biomimetic Nanointerface Made of Multilayered Polyelectrolytes
Authors: Cavelier Sacha , Barrett Christopher J. , Barthelat Francois 
Published: September 2012

AbstractIntegrating organic and inorganic components into hybrid materials is a promising pathway towards unique and useful combinations of stiffness, strength, and toughness. Nature provides superb examples of such materials: bone, teeth, and mollusk shells are made of stiff inorganic mineral inclusions bonded by more compliant proteins and polysaccharides that play a critical role by providing large deformations and energy absorption. Nanometer‐thick polyelectrolyte multilayers (PEMs) provide an elegant approach to mimicking natural organic materials, but experimental data on their mechanical properties is scarce. In this work we have for the first time measured the shear performance and fracture toughness of PEM nanointerfaces that join two silicon substrates. Most of the properties of PEMs fall between those of a typical office tape and an engineering epoxy. However, the energy for failure in shear in PEMs exceeds the other two adhesives by far, because of breakage and reformation of electrostatic bonds. Interestingly, the properties of PEMs can be tuned by, for example, depositing a preliminary (3‐aminopropyl)triethoxysilane layer or by adjusting the degree of hydration. They can also partially heal, and we demonstrate how only a fraction of the initial toughness is lost upon reassembly after fracture. This set of mechanical properties will greatly facilitate the design and optimization of future hybrid materials inspired from nature.
Nanomagnet‐Supported Partially Brominated Manganese–Porphyrin as a Promising Catalyst for the Selective Heterogeneous Oxidation of Hydrocarbons and Sulfides in Water
Authors: Rezaeifard Abdolreza , Jafarpour Maasoumeh , Farshid Parisa , Naeimi Atena 
Published: September 2012

AbstractA novel, magnetically recoverable porphyrin catalyst has been prepared by the coordinative anchoring of the [Mn(Br2TPP)OAc] complex on silica‐coated magnetic nanoparticles (Fe3O4@SiO2, SMNP) through an amine functionality. The heterogeneous catalyst was characterized by powder X‐ray diffraction, transmision electron microscopy, scanning electron microscopy, and FTIR spectroscopy. The catalyst loading on the magnetic support was determined by thermogravimetric (TG) analysis and inductively coupled plasma atomic emission spectroscopy. The catalyst nanoparticles were estimated to have a diameter of less than 10 nm. The TG curve demonstrated that the nanocatalyst was thermally stable up to almost 350 °C, exhibiting high thermostability. The epoxidation of olefins and the oxidation of saturated hydrocarbons to the corresponding ketones as well as sulfides to sulfones in an aqueous solution of tetra‐n‐butylammonium peroxomonosulfate (n‐Bu4NHSO5, TBAOX) were efficiently enhanced with excellent selectivity under the influence of the magnetically separable catalyst. Sulfoxides could also be selectively produced in a mixture of water and ethanol, which makes the title methodology a good alternative for both sulfoxide and sulfone production. The separation and recycling of the catalyst and the byproduct of the oxidant were simple, effective, and economic in this clean oxidation method. FTIR and leaching experiments after seven successive cycles showed that the catalyst was very strongly anchored to the SMNP support.
An Alternative Reaction Outcome in the Gold‐Catalyzed Rearrangement of 1‐Alkynyloxiranes
Authors: González María J. , González Jesús , Vicente Rubén 
Published: September 2012

AbstractThe gold(III)‐catalyzed rearrangement of tetrasubstituted 1‐alkynyloxiranes is described. This transformation led to a different reaction outcome with respect to related substrates previously studied. Thus, tertiary α‐alkynylketones or alkynols can be selectively obtained. Moreover, gold(III) proved capable to catalyze the rearrangement of simple epoxides. These results indicate that gold(III) complexes act as oxophilic Lewis acids rather than π‐acids in these transformations.
A Randomized Clinical Trial of an Identity Intervention Programme for Women with Eating Disorders
Authors: Stein Karen Farchaus , Corte Colleen , Chen Ding‐Geng (Din) , Nuliyalu Ushapoorna , Wing Jeffrey 
Published: September 2012

AbstractObjectiveFindings of a randomized trial of an identity intervention programme (IIP) designed to build new positive self‐schemas that are separate from other conceptions of the self in memory as the means to promote improved health in women diagnosed with eating disorders are reported.MethodAfter baseline data collection, women with anorexia nervosa or bulimia nervosa were randomly assigned to IIP (n = 34) or supportive psychotherapy (SPI) (n = 35) and followed at 1, 6, and 12 months post‐intervention.ResultsThe IIP and supportive psychotherapy were equally effective in reducing eating disorder symptoms at 1 month post‐intervention, and changes were stable through the 12‐month follow‐up period. The IIP tended to be more effective in fostering development of positive self‐schemas, and the increase was stable over time. Regardless of baseline level, an increase in the number of positive self‐schemas between pre‐intervention and 1‐month post‐intervention predicted a decrease in desire for thinness and an increase in psychological well‐being and functional health over the same period.DiscussionA cognitive behavioural intervention that focuses on increasing the number of positive self‐schemas may be central to improving emotional health in women with anorexia nervosa and bulimia nervosa. Copyright © 2012 John Wiley & Sons, Ltd and Eating Disorders Association.
Taxonomic Revision of Annual Species of Astragalus (Fabaceae) in Turkey
Authors: Taeb Fatemeh , Ekici Murat , Podlech Dieter 
Published: September 2012

AbstractA revision of the 17 annual species of Astragalus L. occurring in Turkey is presented. A determination key is provided together with complete descriptions, distribution maps, illustrations of diagnostic floral characters, notes on geography and ecology and an enumeration of all Turkish specimens located (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
3D staggered Lagrangian hydrodynamics scheme with cell‐centered Riemann solver‐based artificial viscosity
Authors: Loubère Raphaël , Maire Pierre‐Henri , Váchal Pavel 
Published: September 2012

SUMMARYThe aim of the present work is the 3D extension of a general formalism to derive a staggered discretization for Lagrangian hydrodynamics on unstructured grids. The classical compatible discretization is used; namely, momentum equation is discretized using the fundamental concept of subcell forces. Specific internal energy equation is obtained using total energy conservation. The subcell force is derived by invoking the Galilean invariance and thermodynamic consistency. A general form of the subcell force is provided so that a cell entropy inequality is satisfied. The subcell force consists of a classical pressure term plus a tensorial viscous contribution proportional to the difference between the node velocity and the cell‐centered velocity. This cell‐centered velocity is an extra degree of freedom solved with a cell‐centered approximate Riemann solver. The second law of thermodynamics is satisfied by construction of the local positive definite subcell tensor involved in the viscous term. A particular expression of this tensor is proposed. A more accurate extension of this discretization both in time and space is also provided using a piecewise linear reconstruction of the velocity field and a predictor‐corrector time discretization. Numerical tests are presented in order to assess the efficiency of this approach in 3D. Sanity checks show that the 3D extension of the 2D approach reproduces 1D and 2D results. Finally, 3D problems such as Sedov, Noh, and Saltzman are simulated. Copyright © 2012 John Wiley & Sons, Ltd.