bluuebunny/crossref_metadata_2025 huggingface dataset:
Advanced Energy‐Storage Architectures Composed of Spinel Lithium Metal Oxide Nanocrystal on Carbon Textiles
Authors: Shen Laifa , Ding Bing , Nie Ping , Cao Guozhong , Zhang Xiaogang
Published: July 2013

Current battery technologies are known to suffer from kinetic problems associated with the solid‐state diffusion of Li+ in intercalation electrodes materials. Not only the use of nanostructure materials but also the design of electrode architectures can lead to more advanced properties. Here, advanced electrode architectures consisting of carbon textiles conformally covered by Li4Ti5O12 nanocrystal are rationally designed and synthesized for lithium ion batteries. The efficient two‐step synthesis involves the growth of ultrathin TiO2 nanosheets on carbon textiles, and subsequent conversion into spinel Li4Ti5O12 through chemical lithiation. Importantly, this novel approach is simple and general, and it is used to successfully produce LiMn2O4/carbon composites textiles, one of the leading cathode materials for lithium ion batteries. The resulting 3D textile electrode, with various advantages including the direct electronic pathway to current collector, the easy access of electrolyte ions, the reduced Li+/e− diffusion length, delivers excellent rate capability and good cyclic stability over the Li‐ion batteries of conventional configurations.
Migratory Insertion of Alkenes into Metal–Oxygen and Metal–Nitrogen Bonds
Authors: Hanley Patrick S. , Hartwig John F.
Published: July 2013

The insertion of an unsaturated ligand into a MC or MH bond proceeds through migratory insertion, a fundamental organometallic reaction. Recent literature documents evidence of the migratory insertion of alkenes into an MO and MN bonds for alkene alkoxylation and alkene amination reactions, respectively. Herein we provide an overview of the literature and a perspective on how these recent experiments relate to classic experiments on CO and CN bond formation with alkene complexes of the late transition metals.
Quantitative analysis of organophosphorus pesticides in freshwater using an optimized firefly luciferase‐based coupled bioluminescent assay
Authors: Marques SM , da Silva JCG Esteves
Published: July 2013

In this paper, a coupled bioluminescent assay, relying on the coupling of the enzymes acetylcholinesterase, S‐acetyl‐coenzyme A synthetase and firefly luciferase, for the detection and quantitation of organophosphorus pesticides, is presented. Using malathion as a model organophosphorus pesticide, the assay was optimized through statistical experimental design methodology, namely Plackett–Burman and central composite designs. The optimized method requires only 20 μL of sample. The linear range for the assay was 2.5–15 μM of malathion, with limits of detection and quantitation of 1.5 and 5.0 μM, respectively. This simple, fast and robust method allows samples to be analyzed at room temperature and without any pretreatment. Copyright © 2013 John Wiley & Sons, Ltd.
Elongation factor P: Function and effects on bacterial fitness
Authors: Doerfel Lili K. , Rodnina Marina V.
Published: July 2013

The elongation phase of translation is promoted by three universal elongation factors, EF‐Tu, EF‐Ts, and EF‐G in bacteria and their homologs in archaea and eukaryotes. Recent findings demonstrate that the translation of a subset of mRNAs requires a fourth elongation factor, EF‐P in bacteria or the homologs factors a/eIF5A in other kingdoms of life. EF‐P prevents the ribosome from stalling during the synthesis of proteins containing consecutive Pro residues, such as PPG, PPP, or longer Pro clusters. The efficient and coordinated synthesis of such proteins is required for bacterial growth, motility, virulence, and stress response. EF‐P carries a unique post‐translational modification, which contributes to its catalytic proficiency. The modification enzymes, which are lacking in higher eukaryotes, provide attractive new targets for the development of new, highly specific antimicrobials. © 2013 Wiley Periodicals, Inc. Biopolymers 99: 837–845, 2013.
A novel self‐assembling peptide with UV‐responsive properties
Authors: Wei Ran , Jin Cheng‐Cheng , Quan Jing , Nie Hua‐li , Zhu Li‐Min
Published: July 2013

A novel heptapeptide comprising Ile‐Gln‐Ser‐Pro‐His‐Phe‐Phe (IQSPHFF) identified and found to undergo self‐assembly into microparticles in solution. To understand the effects of ultraviolet (UV) irradiation on the self‐assembly process, IQSPHFF solutions were exposed to the UV light of 365 nm at room temperature. This exposure was found to have a profound effect on the morphology of the self‐assembled aggregates, converting the microparticles to nanorod shapes. Circular dichroism and FTIR studies indicated distinct structural differences in the arrangements of the peptide moieties before and after UV irradiation. However, Mass spectrum analysis and high performance liquid chromatography of the peptide molecules before and after UV irradiation demonstrated that the chemical structure of IQSPHFF was not changed. UV–visible spectroscopy and fluorescence spectroscopy studies showed that the absorption peak both increased after UV irradiation. Overall, our data show that the heptapeptide with UV‐responsive properties. © 2013 Wiley Periodicals, Inc. Biopolymers 101: 272–278, 2014.
PDMS well platform for culturing millimeter‐size tumor spheroids
Authors: Ratnayaka Sithira H. , Hillburn Taylor E. , Forouzan Omid , Shevkoplyas Sergey S. , Khismatullin Damir B.
Published: July 2013

Multicellular tumor spheroids are widely used as in vitro models for testing of anticancer drugs. The advantage of this approach is that it can predict the outcome of a drug treatment on human cancer cells in their natural three‐dimensional environment without putting actual patients at risk. Several methods were utilized in the past to grow submillimeter‐size tumor spheroids. However, these small models are not very useful for preclinical studies of tumor ablation where the goal is the complete destruction of tumors that can reach several centimeters in diameter in the human body. Here, we propose a PDMS well method for large tumor spheroid culture. Our experiments with HepG2 hepatic cancer cells show that three‐dimensional aggregates of tumor cells with a volume as large as 44 mm3 can be grown in cylindrical PDMS wells after the initial culture of tumor cells by the hanging drop method. This is a 350 times more than the maximum volume of tumor spheroids formed inside hanging drops (0.125 mm3). © 2013 American Institute of Chemical Engineers Biotechnol. Prog., 29:1265–1269, 2013
Effects of Sonocrystallization on the Crystal Size Distribution of Cloxacillin Benzathine Crystals
Authors: Li J. , Bao Y. , Wang J.
Published: July 2013

The effect of ultrasound on the reactive crystallization process of cloxacillin benzathine crystals was investigated to develop a better understanding of the characteristics of this poorly water‐soluble active pharmaceutical ingredient. Characteristics of the products generated under different experimental conditions were compared by offline Malvern Mastersizer measurements and microscopy. The ultrasonic waves applied to reactive crystallization of cloxacillin benzathine were found to be suitable in generating highly regular surface areas for crystal growth. The increased surface areas resulted in decreased average particle sizes and more uniform particles.
Host–Guest Complexation of [60]Fullerenes and Porphyrins Enabled by “Click Chemistry”
Authors: Ho Khanh‐Hy Le , Hijazi Ismail , Rivier Lucie , Gautier Christelle , Jousselme Bruno , de Miguel Gustavo , Romero‐Nieto Carlos , Guldi Dirk M. , Heinrich Benoit , Donnio Bertrand , Campidelli Stéphane
Published: July 2013

Herein the synthesis, characterization, and organization of a first‐generation dendritic fulleropyrrolidine bearing two pending porphyrins are reported. Both the dendron and the fullerene derivatives were synthesized by CuI‐catalyzed alkyne–azide cycloaddition (CuAAC). The electron‐donor–acceptor conjugate possesses a shape that allows the formation of supramolecular complexes by encapsulation of C60 within the jaws of the two porphyrins of another molecule. The interactions between the two photoactive units (i.e., C60 and Zn–porphyrin) were confirmed by cyclic voltammetry as well as by steady‐state and time‐resolved spectroscopy. For example, a shift of about 85 mV was found for the first reduction of C60 in the electron‐donor–acceptor conjugate compared with the parent molecules, which indicates that C60 is included in the jaws of the porphyrin. The fulleropyrrolidine compound exhibits a rich polymorphism, which was corroborated by AFM and SEM. In particular, it was found to form supramolecular fibrils when deposited on substrates. The morphology of the fibrils suggests that they are formed by several rows of fullerene–porphyrin complexes.
Mannose‐Binding Geometry of Pradimicin A
Authors: Nakagawa Yu , Doi Takashi , Taketani Takara , Takegoshi K. , Igarashi Yasuhiro , Ito Yukishige
Published: July 2013

Pradimicins (PRMs) and benanomicins are the only family of non‐peptidic natural products with lectin‐like properties, that is, they recognize D‐mannopyranoside (Man) in the presence of Ca2+ ions. Coupled with their unique Man binding ability, they exhibit antifungal and anti‐HIV activities through binding to Man‐containing glycans of pathogens. Notwithstanding the great potential of PRMs as the lectin mimics and therapeutic leads, their molecular basis of Man recognition has yet to be established. Their aggregate‐forming propensity has impeded conventional interaction analysis in solution, and the analytical difficulty is exacerbated by the existence of two Man binding sites in PRMs. In this work, we investigated the geometry of the primary Man binding of PRM‐A, an original member of PRMs, by the recently developed analytical strategy using the solid aggregate composed of the 1:1 complex of PRM‐A and Man. Evaluation of intermolecular distances by solid‐state NMR spectroscopy revealed that the C2–C4 region of Man is in close contact with the primary binding site of PRM‐A, while the C1 and C6 positions of Man are relatively distant. The binding geometry was further validated by co‐precipitation experiments using deoxy‐Man derivatives, leading to the proposal that PRM‐A binds not only to terminal Man residues at the non‐reducing end of glycans, but also to internal 6‐substituted Man residues. The present study provides new insights into the molecular basis of Man recognition and glycan specificity of PRM‐A.
Understanding the Initial Decomposition Pathways of the n‐Alkane/Nitroalkane Binary Mixture
Authors: Guan Yulei , Zhang Ying , Yi Chunhai , Yang Bolun
Published: July 2013

Addition of nitroalkanes into n‐alkanes can lower the activation barriers of free‐radical production and accelerate the decomposition of n‐alkanes at relatively low temperatures. Four initial decomposition mechanisms of the n‐butane/nitroethane binary mixture were proposed for the promoting effect and considered theoretically at the B3LYP, BB1K, BMK, MPW1K, and M06‐2X levels with MG3S basis set. Energetics above was compared to high‐level CBS‐QB3 and G4 calculations. Calculated results confirm the feasibility of the four initial decomposition pathways: (I) the CNO2 bond rupture of nitroethane to produce ethyl and ·NO2, (II) HONO elimination from nitroethane followed by decomposition to ·OH and ·NO, (III) rearrangement of nitroethane to ethyl nitrite which further dissociates into CH3CH2O· and ·NO, and (IV) direct hydrogen‐abstraction of nitroethane with n‐butane.
Syntheses, Structures and Properties of Four New Transitional Metal Complexes Based on Benzotriazole‐5‐carboxylic Acid
Authors: Li Yang , Sun Changyan , Li Wenjun , Zhou Hualei , Dong Bin
Published: July 2013

Four new complexes, [Zn(btca)(2,2′‐bpy)] (1), [Mn(btca)(2,2′‐bpy)] (2), [Co(btca)(phen)] (3), and [Cu(btca)(phen)] (4), (H2btca=benzotriazole‐5‐carboxylic acid, 2,2′‐bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline), were successfully synthesized and characterized by elemental analysis, single crystal X‐ray diffraction, and IR spectroscopy. Complexes 1–4 crystallize in the orthorhombic system with space group of Pbca and show similar 2D layers, which are interlinked to supramolecular networks by π‐π stacking interactions. Furthermore, TGA curves show that complexes 1–4 have good thermal stability. Solid‐state fluorescent property of complex 1 was also investigated at room temperature.
Iron(III) Chloride Catalyzed Oxidative Coupling Reaction of 1,2‐Diarylethylene Derivatives
Authors: Ji Derong , Su Lidan , Zhao Keqing , Wang Biqin , Hu Ping , Feng Chun , Xiang Shikai , Yang Hua , Zhang Chenggang
Published: July 2013

A nontoxic FeCl3 catalyzed intramolecular oxidative coupling reaction was developed for mild synthesis of a series of phenanthrenes with different substituents. The method involves cross dehydrogenative coupling of a variety of 1,2‐diarylethylene derivatives with di‐tert‐butylperoxide (DTBP) as a sole oxidant at room temperature in CH2Cl2/TFA (9:1 V/V) to yield phenanthrenes in good to excellent yields.
Copper(II)‐Catalyzed Tandem Synthesis of Substituted 3‐Methyleneisoindolin‐1‐ones
Authors: Pan Jie , Xu Zhen , Zeng Runsheng , Zou Jianping
Published: July 2013

An efficient strategy for the synthesis of a variety of 3‐methyleneisoindolin‐1‐ones has been developed. The reaction proceeded from coupling of 2‐iodobenzamides (or 2‐bromobenzamides) and terminal alkynes via Cu(OAc)2·H2O/2,2′‐biimidazole catalyzed in DMF at 60°C and subsequent additive cyclization produced substituted 3‐methyleneisoindolin‐1‐ones in good to excellent yields.
Design and Synthesis of Tri‐substituted Chiral Pyrrolidin‐2‐one Derivatives as CCR4 Antagonists
Authors: Sun Wei , Tian Linjie , Qi Hui , Jiang Dan , Wang Ying , Li Song , Xiao Junhai , Yang Xiaohong
Published: July 2013

A series of tri‐substituted chiral pyrrolidin‐2‐one derivatives have been designed and synthesized as CC chemokine receptor 4 (CCR4) antagonists. The structure of CCR4 was built by homology modeling. Asymmetric synthesis was applied to synthesize the R,R configuration chiral pyrrolidin‐2‐one scaffold. The stereoisomeric configurations of the compounds were identified by 2D 1H‐1H COSY spectroscopy and 1D NOESY spectroscopy. This method was more economical and convenient than traditional X‐ray single crystal diffraction. In addition, the interactions between these compounds and the N‐terminal extracellular tail of CCR4 were studied using capillary zone electrophoresis. The CCR4 chemotaxis inhibition effect was tested in CCR4‐transfected HEK293 cells. Several compounds showed potent activities as CCR4 antagonists. Among these compounds, 1c is the most active one. Its apparent binding constant of CZE experiment result is (1.569±0.11)×105 L·mol−1, and its percentage inhibition of the HEK293/CCR4 cells migration with the concentration of 1 µmol·L−1 in DMSO is 59%. And compound 1f has slightly higher affinity to N‐terminal of CCR4 according to its apparent binding constant than 1b because of the introduced ester linkage. Further studies on the mechanism of these compounds are in progress.
Highly Stereoselective and One‐Pot Synthesis of Tetra‐substituted Monofluoroalkenes with Aldehydes and Fluorobis(phenylsulfonyl)methane
Authors: Shen Xiao , Ni Chuanfa , Hu Jinbo
Published: July 2013

A highly stereoselective synthesis of tetrasubstituted monofluoroalkenes with aldehydes and fluorobis(phenylsulfonyl)methane (FBSM) in one pot has been developed. The reaction was amenable to para‐ and meta‐substituted aryl aldehydes, 2‐naphthaldehyde, and cinnamaldehyde, giving phenylsulfonyl‐substituted monofluoroalkenes in 40%–86% yields with 98/2–99/1 Z/E ratios. The presence of the sulfonyl group enables the further transformation of the products into more useful monofluoroalkenes.
Regioselective Synthesis of 2,6‐Dimethyl‐3,5‐bis[(3‐aryl‐5‐trifluoromethyl)‐isoxazol‐4‐carbonyl]‐pyridine Derivatives
Authors: Yang Yindi , Zhang Min , Zhu Yiwen , Zhang Li , Xie Qiqiang , Song Liping , Deng Hongmei
Published: July 2013

Ethyl 4,4,4‐trifluoro‐3‐oxo‐butyrate reacted with 2,6‐dimethyl‐3,5‐diacetyl‐pyridine 1 in the presence of NaOC2H5 at 0°C to give 2,6‐dimethyl‐3,5‐bis(4,4,4‐trifluoro‐1,3‐oxo‐butyl)‐pyridine (2a) in good yield. Cyclization reaction of 2a and aryl imidoyl chlorides 5a–5i, obtained from chlorination of aryl oximes with N‐chlorosuccimide, afforded 2,6‐dimethyl‐3,5‐bis[(3‐aryl‐5‐trifluoromethyl)‐isoxazol‐4‐carbonyl]‐pyridine derivatives 6a–6i.
Chemical, Pharmacological, and in vitro Metabolic Stability Studies on Enantiomerically Pure RC‐33 Compounds: Promising Neuroprotective Agents Acting as σ1 Receptor Agonists
Authors: Rossi Daniela , Pedrali Alice , Gaggeri Raffaella , Marra Annamaria , Pignataro Luca , Laurini Erik , Dal Col Valentina , Fermeglia Maurizio , Pricl Sabrina , Schepmann Dirk , Wünsch Bernhard , Peviani Marco , Curti Daniela , Collina Simona
Published: July 2013

Our recent research efforts identified racemic RC‐33 as a potent and metabolically stable σ1 receptor agonist. Herein we describe the isolation of pure RC‐33 enantiomers by chiral chromatography, assignment of their absolute configuration, and in vitro biological studies in order to address the role of chirality in the biological activity of these compounds and their metabolic processing. The binding of enantiopure RC‐33 to the σ1 receptor was also investigated in silico by molecular dynamics simulations. Both RC‐33 enantiomers showed similar affinities for the σ1 receptor and appeared to be almost equally effective as σ1 receptor agonists. However, the R‐configured enantiomer showed higher in vitro hepatic metabolic stability in the presence of NADPH than the S enantiomer. Overall, the results presented herein led us to select (R)‐RC‐33 as the optimal candidate for further in vivo studies in an animal model of amyotrophic lateral sclerosis.
Caspofungin exposure‐response relationships in adult patients with mucosal or invasive candidiasis
Authors: Comisar Wendy , Sun Peng , Li Susan , Sable Carole , Schwartz Michael , Bi Sheng , Chow Joseph , Ngai Angela , Winchell Gregory , Kartsonis Nicholas , Stone Julie
Published: July 2013

Caspofungin is an echinocandin antifungal agent administered once daily as an intravenous infusion. Relationships between caspofungin exposure and clinical efficacy and safety were investigated. End‐of‐infusion (CEOI) and trough (C24 hours) concentrations were obtained in 218 patients with mucosal (i.e., esophageal and/or oropharyngeal) candidiasis (MC) receiving caspofungin 35, 50, or 70 mg/day and 278 patients with invasive candidiasis (IC) receiving 50, 100, or 150 mg/day. Area under the plasma concentration–time curve (AUC0–24 hours) was obtained in a subset of MC patients (n = 99). Odds ratios were estimated for the association between log‐transformed PK and efficacy response and the occurrence of common adverse events. No pharmacokinetic or hybrid parameter (ratio of AUC:MIC, CEOI:MIC, C24 hours:MIC) was significantly correlated with overall treatment outcome in either MC or IC, although this patient population may exhibit confounding factors which masked a potential pharmacokinetic/pharmacodynamic relationship. An exploratory evaluation of MC identified significant pharmacokinetic correlations with endoscopic response, but not symptom response. Statistically significant associations were identified for IC patients with C. parapsilosis infections. Occurrence of clinical adverse events and/or laboratory abnormalities did not appear to be increased by higher caspofungin plasma concentrations. Caspofungin concentrations achieved with 50 mg/day are generally within the therapeutic window for the treatment of candidiasis.
Ultrafast Dynamics of meso‐Tetraphenylmetalloporphyrins: The Role of Dark States
Authors: Liang Yu , Bradler Maximilian , Klinger Melanie , Schalk Oliver , Balaban Mihaela Carmen , Balaban Teodor Silviu , Riedle Eberhard , Unterreiner Andreas‐Neil
Published: July 2013

Studying the relaxation pathways of porphyrins and related structures upon light absorption is crucial to understand the fundamental processes of light harvesting in biosystems and many applications. Herein, we show by means of transient absorption studies, following Q‐ and Soret‐band excitation, and ab initio calculations on meso‐tetraphenylporphyrinato magnesium(II) (MgTPP) and meso‐tetraphenylporphyrinato cadmium(II) (CdTPP) that electronic relaxation following Soret‐band excitation of porphyrins with a heavy central atom is mediated by a hitherto disregarded dark state. This accounts for an increased rate of internal conversion. The dark state originates from an orbital localized at the central nitrogen atoms and its energy continuously decreases along the series from magnesium to zinc to cadmium to below 2.75 eV for CdTPP dissolved in tetrahydrofuran. Furthermore, we are able to directly trace fast intersystem crossing in the cadmium derivative, which takes place within (110±20) ps.
Linear circuits: a measurement‐based approach
Authors: Mohsenizadeh Navid , Nounou Hazem , Nounou Mohamed , Datta Aniruddha , Bhattacharyya Shankar P.
Published: July 2013

This paper proposes a new measurement‐based approach that can solve synthesis problems in unknown linear circuits. The method makes use of a small number of measurements to determine the functional dependency of any circuit signal or variable on any set of design variables. Once the functional dependency is obtained, the design requirements can be applied to find the design parameter values. The results are described for linear direct current and alternating current circuits. Copyright © 2013 John Wiley & Sons, Ltd.
Inducible gene expression in fetal thymic epithelium: A new BAC transgenic model
Authors: Fiorini Emma , Ferrero Isabel , Poisson Caroline , Scarpellino Leonardo , Luther Sanjiv Andreas , MacDonald H. Robson
Published: July 2013

The thymus is the site of T cell development. Several stromal and hematopoietic cell types are necessary for the proper function of thymic selection and eventually peripheral immunity. Thymic epithelial cells (TECs) are essential for T cell lineage commitment, expansion, and maturation in the thymus. We were interested in developing an in vivo model in which exogenous gene expression could be transiently induced in embryonic TEC (Tet‐On system). To this end, we have generated a bacterial artificial chromosome (BAC) transgenic mouse line in which the reverse tetracycline‐dependent transactivator (rtTA) is expressed under the control of the Foxn1 promoter, a transcriptional factor indispensable for TEC development. To analyze the expression pattern and efficiency of this novel mouse model, we crossed the Foxn1‐rtTA founder with a Tet‐Responsive Element (TRE)‐LacZ GFP mouse reporter to obtain a double transgenic mouse. In the presence of doxycycline, rtTA can interact with TRE and induce the expression of GFP and LacZ. In this double transgenic mouse, we observed that GFP expression was high, inducible and limited to TEC in fetal thymus. In contrast, in adult thymus, when TEC development and maturation is completed, GFP was barely detectable. Therefore, Foxn1‐rtTA represents a new and efficient transgenic mouse model to induce genes of interest specifically in fetal thymic epithelium. genesis 51:717–724. © 2013 Wiley Periodicals, Inc.
Neuropsychological functioning in adolescents with anorexia nervosa before and after cognitive remediation therapy: A feasibility trial
Authors: Dahlgren Camilla Lindvall , Lask Bryan , Landrø Nils Inge , Rø Øyvind
Published: July 2013

Objective

To investigate neuropsychological functioning in adolescents with anorexia nervosa (AN) before and after receiving cognitive remediation therapy (CRT).

Method

Twenty young females with AN participated in an individually‐delivered CRT treatment program. Neuropsychological and psychiatric assessments were administered before and after treatment. Weight, depression, anxiety, duration of illness, and level of eating disorder psychopathology were considered as covariates in statistical analyses.

Results

Significant changes in weight, depression, visio‐spatial memory, perceptual disembedding abilities, and verbal fluency were observed. Changes in weight had a significant effect on improvements in visuo‐spatial memory and verbal fluency. Results also revealed a significant effect of depressive symptoms on perceptual disembedding abilities.

Discussion

The results suggest improvements on a number of neuropsychological functions during the course of CRT. Future studies should explore the use of additional assessment instruments, and include control groups to assess the effectiveness of the intervention. © 2013 Wiley Periodicals, Inc. (Int J Eat Disord 2013; 46:576–581)
Pyridinediimine Iron Dicarbonyl Complexes with Pendant Lewis Bases and Lewis Acids Located in the Secondary Coordination Sphere
Authors: Thammavongsy Zachary , LeDoux Micah E. , Breuhaus‐Alvarez Andrew G. , Seda Takele , Zakharov Lev N. , Gilbertson John D.
Published: July 2013

A series of asymmetric iron(II) dichloride and dicarbonyl pyridinediimine (PDI) complexes that contain either pendant Lewis bases or Lewis acids located in the secondary coordination sphere were synthesized. These complexes are important intermediates in the reduction scheme of the small molecule CO2 on iron(II). The electrochemistry of the direduced FePDI(CO)2 complexes was evaluated for the 2‐electron oxidation from the reduced‐ligand to the neutral‐ligand species. The complexes with either pendant Lewis bases or Lewis acids located in the secondary coordination sphere displayed reduction potentials for CO release that span over 300 mV.
Efficient and Rapid Synthesis of Chlorido‐Bridged Half‐Sandwich Complexes of Ruthenium, Rhodium, and Iridium by Microwave Heating
Authors: Tönnemann Justus , Risse Julie , Grote Zacharias , Scopelliti Rosario , Severin Kay
Published: July 2013

The dinuclear complexes [(p‐cymene)RuCl2]2 and [(cyclopentadienyl)MCl2]2 (M = Ru, Rh, Ir) are important starting materials in organometallic chemistry. The standard synthesis of these complexes involves heating of an alcoholic solution of RuIII, RhIII, or IrIII salts with precursors of the π‐ligands for several hours under reflux. Microwave heating allows these complexes to be obtained within a few minutes without compromising the yields. Furthermore, the microwave‐assisted syntheses require less solvent and, in some cases, lower amounts of ligand precursors.
Chemical and thermal evaluation of olive oil refining at different oxidative levels
Authors: Caponio Francesco , Chiavaro Emma , Paradiso Vito Michele , Paciulli Maria , Summo Carmine , Cerretani Lorenzo , Gomes Tommaso
Published: July 2013

In this work, differential scanning calorimetry (DSC) was for the first time applied to evaluate cooling and heating curves and related thermal properties of olive oil during refining process steps starting from two series of samples at different initial peroxide values (low, 15 meq O2/kg and high, 30 meq O2/kg). Thermal properties were statistically correlated by means of principal component analysis (PCA) to those substance classes (products deriving from oxidation, polymerization and hydrolysis of triacylglycerols (TAG)) that could exert adverse effects on consumer health and a negative contribution to the shelf‐life of the refined oil. A concomitant significant increase of K270 and polymerized TAG, as a general decrease of oxidation level was exhibited by oils during bleaching. Crystallization significantly shifted towards lower temperatures as well as onset temperature of heating, enlarging transition range, starting from bleaching and at both oxidation levels. PCA was performed to tentatively discriminate among samples according to different refining steps and/or initial level of oxidation correlating thermal properties and chemical results. The first principal component clearly clustered samples according to different refining steps and this differentiation was possible on the basis of the relation of thermal parameters with polymerized TAG conjugated dienes and trienes (K232 and K270, respectively). This preliminary goal should lead to deepen the study of DSC application in the evaluation of the quality of olive and other vegetable oils during refining.

Practical applications: DSC is a thermal technique that nowadays covers a large set of applications in lipid technology due to its indisputable advantages as it does not require sample preparation and use of solvents, resulting in a reduced environmental impact. The preliminary findings of this study promote the application of the technique in the evaluation of olive oil quality during refining steps in relation with molecular species formed as polymerized TAG and conjugated trienes discriminating crude and neutralized samples to bleached and deodorized oils. DSC could be also applied on other vegetable oils where refining process is more frequently applied.
Platinum‐Based Heterogeneously Catalyzed Hydrosilylation
Authors: Pagliaro Mario , Ciriminna Rosaria , Pandarus Valerica , Béland François
Published: July 2013

Efficient and recyclable solid catalysts for the hydrosilylation of olefins are highly desirable, both to reduce the economic and environmental costs of traditional homogeneous processes and to improve the health properties of products that find a number of uses in daily life. In this account we critically review selected examples amongst the numerous platinum‐based materials developed in the last decade, with the goal of identifying important challenges in this relevant domain of synthetic organic chemistry.
Sodium Borohydride Reduction of Carbamoyl Azide Function: A Synthesis of N‐Protected N′‐Formyl‐gem‐diaminoalkyl Derivatives
Authors: Verardo Giancarlo , Gorassini Andrea
Published: July 2013

A simple, efficient two‐step synthesis of N‐protected N′‐formyl‐gem‐diaminoalkyl derivatives is reported. The procedure involves the unprecedented reduction of the carbamoyl azide of α‐N‐Boc/Fmoc/Z‐protected amino acids and dipeptides (Boc = tert‐butoxycarbonyl, Fmoc = 9‐fluorenylmethoxycarbonyl, Z = benzyloxycarbonyl) by treatment with NaBH4 at room temperature. The reaction proceeds rapidly (45 min) without detectable epimerization (by HPLC‐ESI‐MS analysis) and is not influenced by the nature of the starting carbamoyl azide. The 1H and 13C NMR analyses of the synthesized N‐protected N′‐formamides were carried out in [D6]DMSO. The spectra exhibited the presence of two rotameric forms in solution as a result of the restricted rotation around the N–CO formyl bond. The integration of the N–CH–N protons of the two isomers showed that the cis isomer (rotamer B) was the more abundant conformer by 60 to 78 %. The reported synthesis represents the potential value of carbamoyl azides as versatile chiral starting materials for many synthetic purposes.
Angiogenesis genes, dietary oxidative balance and breast cancer risk and progression: The breast cancer health disparities study
Authors: Slattery Martha L. , John Esther M. , Torres‐Mejia Gabriela , Lundgreen Abbie , Lewinger Juan Pablo , Stern Mariana C. , Hines Lisa , Baumgartner Kathy B. , Giuliano Anna R. , Wolff Roger K.
Published: July 2013

Angiogenesis is essential for tumor development and progression. Genetic variation in angiogenesis‐related genes may influence breast carcinogenesis. We evaluated dietary factors associated with oxidative balance, DDIT4 (one SNP), FLT1 (35 SNPs), HIF1A (four SNPs), KDR (19 SNPs), MPO (one SNP), NOS2A (15 SNPs), TEK (40 SNPs) and VEGFA (eight SNPs) and breast cancer risk among Hispanic (2,111 cases and 2,597 controls) and non‐Hispanic white (1,481 cases and 1,586 controls) women in the Breast Cancer Health Disparities Study. Adaptive rank truncated product (ARTP) analysis was used to determine gene and pathway significance with breast cancer. TEK was associated with breast cancer overall (pARTP = 0.03) and with breast cancer survival (pARTP = 0.01). KDR was of borderline significance overall (pARTP = 0.07), although significantly associated with breast cancer in both low and intermediate Native American (NA) ancestry groups (pARTP = 0.02) and estrogen receptor (ER)+/progesterone receptor (PR)− tumor phenotype (pARTP = 0.008). Both VEGFA and NOS2A were associated with ER−/PR− tumor phenotype (pARTP = 0.01 and pARTP = 0.04, respectively). FLT1 was associated with breast cancer survival among those with low NA ancestry (pARTP = 0.009). With respect to diet, having a higher dietary oxidative balance score (DOBS) was significantly associated with lower breast cancer risk [odds ratio (OR) 0.74, 95% confidence interval (CI) 0.64–0.84], with the strongest associations observed for women with the highest NA ancestry (OR 0.44, 95% CI 0.30–0.65). We observed few interactions between DOBS and angiogenesis‐related genes. Our data suggest that dietary factors and genetic variation in angiogenesis‐related genes contribute to breast cancer carcinogenesis.
Sickle cell trait is not associated with endemic Burkitt lymphoma: An ethnicity and malaria endemicity‐matched case–control study suggests factors controlling EBV may serve as a predictive biomarker for this pediatric cancer
Authors: Mulama David H. , Bailey Jeffrey A. , Foley Joslyn , Chelimo Kiprotich , Ouma Collins , Jura Walter G.Z.O. , Otieno Juliana , Vulule John , Moormann Ann M.
Published: July 2013

Endemic Burkitt lymphoma (eBL) is associated with Epstein–Barr virus (EBV) and Plasmodium falciparum coinfections. Malaria appears to dysregulate immunity that would otherwise control EBV, thereby contributing to eBL etiology. Juxtaposed to human genetic variants associated with protection from malaria, it has been hypothesized that such variants could decrease eBL susceptibility, historically referred to as “the protective hypothesis.” Past studies attempting to link sickle cell trait (HbAS), which is known to be protective against malaria, with protection from eBL were contradictory and underpowered. Therefore, using a case–control study design, we examined HbAS frequency in 306 Kenyan children diagnosed with eBL compared to 537 geographically defined and ethnically matched controls. We found 23.8% HbAS for eBL patients, which was not significantly different compared to 27.0% HbAS for controls [odds ratio (OR) = 0.85; 95% confidence interval (CI) 0.61–1.17; p‐value = 0.33]. Even though cellular EBV titers, indicative of the number of latently infected B cells, were significantly higher (p‐value < 0.0003) in children residing in malaria holoendemic compared to hypoendemic areas, levels were not associated with HbAS genotype. Combined, this suggests that although HbAS protects against severe malaria and hyperparasitemia, it is not associated with viral control or eBL protection. However, based on receiver operating characteristic curves factors that enable the establishment of EBV persistence, in contrast to those involved in EBV lytic reactivation, may have utility as an eBL precursor biomarker. This has implications for future human genetic association studies to consider variants influencing control over EBV in addition to malaria as risk factors for eBL.
Efficient optimization of van der Waals parameters from bulk properties
Authors: Burger Steven K. , Cisneros G. Andrés
Published: July 2013

Due to the computational cost involved, when developing a force field for new compounds, one often avoids fitting van der Waals (vdW) terms, instead relying on a general force field based on the atom type. Here, we provide a novel approach to efficiently optimize vdW terms, based on bothab initiodimer energies and condensed phase properties. The approach avoids the computational challenges of searching the parameter space by using an extrapolation method to obtain a reliable difference quotient for the parameter derivatives based on the central difference. The derivatives are then used in an active‐space optimization method which convergences quadratically. This method is applicable to polarizable and nonpolarizable force fields, although we focus on the parameterization of the AMBER force field. The scaling of the electrostatic potential (ESP) of the compounds is also studied. The algorithm is tested on 12 compounds, reducing the root mean squared error (RMSE) of the density from 0.061 g/cm3with GAFF parameters to 0.004 g/cm3, and the heat of vaporization from 1.13 to 0.05 kcal/mol. This is done with only four iterations of molecular dynamic runs. Using the optimized vdW parameters, the RMSE of the self‐diffusionwas reduced from 1.22 × 10−9to 0.78 × 10−9m2s−1and the RMSE of the hydration free energieswas reduced from 0.30 to 0.26 kcal/mol. Scaling the ESP to improve dimer energies resulted in theRMSE improving to 0.77× 10−9m2s−1, but theworsened to 0.33 kcal/mol. © 2013 Wiley Periodicals, Inc.
Shoaling internal solitary waves
Authors: Sutherland B. R. , Barrett K. J. , Ivey G. N.
Published: July 2013

The evolution and breaking of internal solitary waves in a shallow upper layer as they approach a constant bottom slope is examined through laboratory experiments. The waves are launched in a two‐layer fluid through the standard lock‐release method. In most experiments, the wave amplitude is significantly larger than the depth of the shallow upper layer so that they are not well described by Korteweg‐de Vries theory. The dynamics of the shoaling waves are characterized by the Iribarren number, Ir, which measures the ratio of the topographic slope to the square root of the characteristic wave slope. This is used to classify breaking regimes as collapsing, plunging, surging, and nonbreaking for increasing values of Ir. For breaking waves, the maximum interface descent,
, is predicted to depend upon the topographic slope, s, and the incident wave's amplitude and width, Asw and Lsw, respectively, as
. This prediction is corroborated by our experiments. Likewise, we apply simple heuristics to estimate the speed of interface descent, and we characterize the speed and range of the consequent upslope flow of the lower layer after breaking has occurred.
Role of leptin in legg–calvé–perthes disease
Authors: Lee Ju‐Hyung , Zhou Lu , Kwon Keun‐Sang , Lee Dongwook , Park Byung‐Hyun , Kim Jung Ryul
Published: July 2013

Obesity is considered a clinical risk sign for Legg–Calvé–Perthes disease (LCPD). Leptin is primarily secreted by adipocytes, and it regulates adipose tissue mass and body weight. Furthermore, obesity is clearly associated with increased leptin levels. We investigated the roles of leptin and the soluble leptin receptor (sOB‐R) in LCPD. This matched case–control study included 38 male and 3 female patients with LCPD, and an equal number of age—(range was 4–12) and sex‐matched control patients with healthy fractures. Serum leptin and sOB‐R levels were quantified with ELISA. The free leptin index (FLI) was defined as the ratio of leptin to sOB‐R levels. Serum leptin levels, sOB‐R, and FLI were compared between groups. The relationship between leptin, disease severity, and treatment outcomes were analyzed in the LCPD group. There were no significant differences between groups in terms of age, sex, and body mass index (BMI) percentile. Mean leptin levels (p = 0.042), sOB‐R levels (p = 0.003), and FLI (p = 0.013) differed significantly between groups. In the LCPD group, the serum leptin levels, sOB‐R levels, and FLI differed significantly between the lateral pillar and Stulberg classification groups (p < 0.05). Also, the leptin levels and FLI increased significantly according to the lateral pillar and Stulberg classifications even after adjusting for age and BMI percentile (p < 0.05). Circulating leptin and FLI were significantly higher in the LCPD group. Furthermore, leptin, disease severity, and treatment outcomes were associated. This correlation suggests that leptin might play an important role in LCPD pathogenesis. © 2013 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 31:1605‐1610, 2013
SERS study on surface chain geometry of atactic poly (methyl methacrylate) film and nanosphere
Authors: Hu Chenglong , Chen Shaoyun , Zhang Weihong , Xie Fangyan , Chen Jian , Chen Xudong
Published: July 2013

The surface chain geometry of atactic poly (methyl methacrylate) (a‐PMMA) film and nanosphere (NS) was revealed by surface‐enhanced Raman scattering (SERS) spectra. The Ag nanoparticles and nanoplates were prepared by electrochemical deposition and chemical synthesis for SERS substrates. The experimental results suggested that the molecular chain axis of a‐PMMA film adopted a trans‐conformation on bonding to Ag surface ascribed to the short‐range chemical (CHEM) effect according to the SERS selection rules. However, for the well‐coated monolayer of a‐PMMA NSs, the α‐CH3 in polymer chains stood vertically to the Ag surface due to the giant local electromagnetic effect, then the chain conformation presented in the interface between a‐PMMA NSs and Ag metal was adopted the opposite orientation compared with a‐PMMA film. The Raman enhancement of the Ag nanoparticles was more prominent than that of the Ag nanoplates due to the free energies of face‐centered cubic crystal faces in nanoparticles, but the single crystals with (111) plane of Ag nanoplates could improve the stability of SERS signals when the annealed temperature was above Tg of a‐PMMA NSs. The present work can provide some useful information of surface chain geometry and conformation of NSs for designing various materials with well‐defined structure via a‐PMMA NSs template. Copyright © 2013 John Wiley & Sons, Ltd.
Molecular Design, Structures, and Activity of Antimicrobial Peptide‐Mimetic Polymers
Authors: Takahashi Haruko , Palermo Edmund F. , Yasuhara Kazuma , Caputo Gregory A. , Kuroda Kenichi
Published: July 2013

There is an urgent need for new antibiotics which are effective against drug‐resistant bacteria without contributing to resistance development. We have designed and developed antimicrobial copolymers with cationic amphiphilic structures based on the mimicry of naturally occurring antimicrobial peptides. These copolymers exhibit potent antimicrobial activity against a broad spectrum of bacteria including methicillin‐resistant Staphylococcus aureus with no adverse hemolytic activity. Notably, these polymers also did not result in any measurable resistance development in E. coli. The peptide‐mimetic design principle offers significant flexibility and diversity in the creation of new antimicrobial materials and their potential biomedical applications.
Social Pressure at the Plate: Inequality Aversion, Status, and Mere Exposure
Authors: Mills Brian M.
Published: July 2013

This paper uses professional baseball data to evaluate the impact of social pressures on subjective decisions made by officials. Umpires show tendencies consistent with both centrality bias and favoritism toward players with higher status in the league. Results also indicate that the odds of a strike are lower for batters in close proximity to the official throughout the game. Implications extend beyond sport to issues regarding closeness of contact in employee–manager relationships and pay and promotions decisions in the workplace. Given the persistent monitoring of officials in professional baseball, this phenomenon could be more prevalent in less scrutinized positions in other industries. Copyright © 2013 John Wiley & Sons, Ltd.
Preparation and characterization of nanometer‐thin freestanding polymer foils for laser‐ion acceleration
Authors: Aurand Bastian , Elkin Bentsian , Heim Lars‐Oliver , Lommel Bettina , Kindler Birgit , Tomut Marilena , Rödel Christian , Kuschel Stephan , Jäckel Oliver , Barz Jakob , Kuehl Thomas
Published: July 2013

We report on the production and characterization of polymer‐based ultra‐thin (sub 10 nm) foils suited for experiments on laser‐ion acceleration in the regime of radiation pressure acceleration. Beside the remarkable mechanical stability compared with commonly used diamond‐like‐carbon foils, a very homogeneous layer thickness and a small surface roughness have been achieved. We describe the technical issues of the production process as well as detailed studies of the mechanical stability and surface roughness tests. The capability of producing uniform targets of large area is essential for advanced laser‐ion acceleration projects which are dealing with high repetition rate and extended measurement series, but might also be useful for other applications which require ultra‐thin and freestanding substrates of high quality. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1355–1360
2012 President's Plenary International Psycho‐Oncology Society: future directions in psycho‐oncology
Authors: Breitbart W. , Bultz B. D. , Dunn J. , Grassi L. , Watson M.
Published: July 2013

The inaugural President's Plenary was held at the 2012 International Psycho‐oncology Society's World Congress in Brisbane to provide a platform for dissemination of important initiatives and achievements of interest to cancer professionals globally. The vision of the International Psycho‐oncology Society – clarified and defined in 2004 – is that all cancer patients and their families throughout the world should receive optimal psychosocial care at all stages of disease and survivorship. Recent initiatives have been driven by the need to see psychosocial care available as a seamless part of holistic multidisciplinary quality cancer care and life‐extending lifestyle changes promoted and supported through the expertise of behavioural and social scientists. In keeping with World Health Organization targets that there is ‘no health without mental health’, cancer health must include mental health. This is in line with the patients' declaration to ‘See us – not our disease’. The aim is to ensure that within the next decade, psychosocial care is acknowledged as a vital part of the patient journey and accepted globally as good practice within cancer care. The President's Plenary session covered the need for the following:

Behavioural and social scientists to be integral to the planned lifestyle changes that the United Nations agreed, at a high‐level meeting in 2011, to reduce world cancer incidence and morbidity over the next decade;

An internationally agreed standard of quality cancer care that includes psychosocial care for patients and their families and carers;

An endorsement to assess distress as the 6th vital sign;

A declaration that mental health within cancer health is a human right;

Psycho‐oncology professionals to integrate into a federation promoting better national and international outcomes; strength in numbers speaking with a unified voice.

The aim is to encourage dialogue between all cancer professionals and patient representatives to progress these targets; everyone has a voice. Copyright © 2013 John Wiley & Sons, Ltd.
DFT calculations of phonons in GaAs with zinc blende and wurtzite structures
Authors: Petrova N. V. , Yakovkin I. N.
Published: July 2013

The phonon bands of GaAs with zinc blende and wurtzite structures have been calculated by DFT method. The estimated phonon frequencies at the center of Brillouin zone are compared with results of recent Raman spectroscopy studies of GaAs nanowires, where the formation of the wurtzite structure is favorable. Present calculations confirm the assignments of the peaks in the spectra to transfer optical (TO) and longitudinal optical (LO) phonon modes in wurtzite structure in forming GaAs nanowires.