bluuebunny/crossref_metadata_2025 huggingface dataset:
Highly Efficient Asymmetric Epoxidation of Electron‐Deficient α,β‐Enones and Related Applications to Organic Synthesis
Authors: Zheng Changwu , Li Yawen , Yang Yingquan , Wang Haifeng , Cui Haifeng , Zhang Junkang , Zhao Gang
Published: July 2009

The asymmetric epoxidation of electron‐deficient olefins has been achieved using inexpensive and readily available prolinols as catalysts with good to excellent yields and enantioselectivities. The utility of the resulting chiral epoxides was illustrated by elaboration to several synthetically useful compounds featuring a concise synthesis of (−)‐(5R,6S)‐balasubramide.
Efficient Copper‐Catalyzed Synthesis of N‐Alkylanthranilic Acids via an ortho‐Substituent Effect of the Carboxyl Group of 2‐Halobenzoic Acids at Room Temperature
Authors: Zeng Liang , Fu Hua , Qiao Renzhong , Jiang Yuyang , Zhao Yufen
Published: July 2009

We have developed an efficient copper‐catalyzed method for the synthesis of N‐alkylanthranilic acids. The protocol uses inexpensive copper(I) iodide/racemic 1,1′‐binaphthyl‐2,2′‐diol (rac‐BINOL) as the catalyst/ligand system, readily available 2‐halobenzoic acids and aliphatic amines as the starting materials, the coupling reactions were performed at room temperature, and various functionalities in the substrates were tolerated.
Gold‐Catalyzed Intermolecular Reactions of (Z)‐Enynols with Indoles for the Construction of Dihydrocyclohepta[b]indole Skeletons through a Cascade Friedel–Crafts/Hydroarylation Sequence
Authors: Lu Yuhua , Du Xiangwei , Jia Xueshun , Liu Yuanhong
Published: July 2009

An efficient domino approach for the synthesis of indole‐fused carbocycles and their analogues from the reactions of suitably substituted (Z)‐enynols with indoles or pyrroles under mild reaction conditions was developed. This methodology is realized by a tandem reaction using Au/Ag catalysts, which could catalyze both of the Friedel–Crafts and the hydroarylation reaction in the same vessel.
Regioselective Synthesis of Phenols and Halophenols from Arylboronic Acids Using Solid Poly(N‐vinylpyrrolidone)/ Hydrogen Peroxide and Poly(4‐vinylpyridine)/Hydrogen Peroxide Complexes
Authors: Prakash G. K. Surya , Chacko Sujith , Panja Chiradeep , Thomas Tisa Elizabeth , Gurung Laxman , Rasul Golam , Mathew Thomas , Olah George A.
Published: July 2009

Solid hydrogen peroxide complexes based on poly(N‐vinylpyrrolidone) and poly(4‐vinylpyridine) were prepared and used as solid hydroxylating reagents. These solid hydrogen peroxide equivalents are found to be much safer, convenient and efficient reagent systems for the ipso‐hydroxylation of arylboronic acids to the corresponding phenols in high yields at a faster rate. The versatility of the reagents has been further expanded for the one‐pot synthesis of halophenols. Density functional theory calculations were carried out on hydrogen peroxide complexes of N‐ethylpyrrolidone and 4‐ethylpyridine as models to get a better understanding of structure and behavior of hydrogen peroxide complexes of the polymers poly(N‐vinylpyrrolidone) and poly(4‐vinylpyridine) compared to aqueous hydrogen peroxide.
Modular Furanoside Phosphite‐Phosphoroamidites, a Readily Available Ligand Library for Asymmetric Palladium‐Catalyzed Allylic Substitution Reactions. Origin of Enantioselectivity
Authors: Raluy Eva , Pàmies Oscar , Diéguez Montserrat
Published: July 2009

A library of furanoside phosphite‐phosphoroamidite ligands has been synthesized and screened in the palladium‐catalyzed allylic substitution reactions of several substrate types. These series of ligands can be prepared efficiently from easily accessible D‐xylose and D‐glucose. Their modular nature enables the position of the phosphoroamidite group, configuration of C‐3 of the furanoside backbone and the substituents/configurations in the biaryl phosphite/phosphoroamidite moieties to be easily and systematically varied. By carefully selecting the ligand components, therefore, high regio‐ and enantioselectivities (ees up to 98%) and good activities have been achieved in a broad range of mono‐ and disubstituted hindered and unhindered linear and cyclic substrates. The NMR studies on the palladium‐π‐allyl intermediates provide a deeper understanding about the effect of the ligand parameters on the origin of enantioselectivity. They also indicate that the nucleophilic attack takes place predominantly at the allylic terminal carbon atom located trans to the phosphoroamidite moiety.
Micellar Effects in Olefin Hydroformylation Catalysed by Neutral, Calix[4]arene‐Diphosphite Rhodium Complexes
Authors: Monnereau Laure , Sémeril David , Matt Dominique , Toupet Loïc
Published: July 2009

The combination of calixarene‐derived surfactants and neutral rhodium complexes containing a hemispherical “1,3‐calix‐diphosphite” ligand led to efficient catalysts for the hydroformylation of octene and other olefins in water. While the surfactants allowed the formation of micelles that dissolve both the catalyst and the alkene, thereby resulting in high olefin:rhodium ratios, the diphosphite provided a tight envelope about the catalytic centre able to drive the reaction towards the linear aldehydes. Best results in the hydroformylation of 1‐octene were obtained when using [tetra(p‐sulfonato)]‐(tetra‐n‐butoxy)‐calix[4]arene as surfactant. With this additive remarkable linear to branched aldehyde ratios of up to 62 were obtained, the corresponding activities being higher than those observed when operating in an organic solvent [turnover frequencies (TOFs) up to 630 mol(converted 1‐octene)⋅ mol(Rh)−1⋅h−1].
Cationic Ruthenium‐Cyclopentadienyl‐Diphosphine Complexes as Catalysts for the Allylation of Phenols with Allyl Alcohol; Relation between Structure and Catalytic Performance in O‐ vs. C‐Allylation
Authors: van Rijn Jimmy A. , Lutz Martin , von Chrzanowski Lars S. , Spek Anthony L. , Bouwman Elisabeth , Drent Eite
Published: July 2009

A new catalytic method has been investigated to obtain either O‐ or C‐allylated phenolic products using allyl alcohol or diallyl ether as the allyl donor. With the use of new cationic ruthenium(II) complexes as catalyst, both reactions can be performed with good selectivity. Active cationic Ru(II) complexes, having cyclopentadienyl and bidentate phosphine ligands are generated from the corresponding Ru(II) chloride complexes with a silver salt. The structures of three novel (diphosphine)Ru(II)CpCl catalyst precursor complexes are reported. It appears that the structure of the bidentate ligand has a major influence on catalytic activity as well as chemoselectivity. In addition, a strong cocatalytic effect of small amounts of acid is revealed. Model experiments are described that have been used to build a reaction network that explains the origin and evolution in time of both O‐allylated and C‐allylated phenolic products. Some mechanistic implications of the observed structure vs. performance relation of the [(diphosphine)RuCp]+ complexes and the cocatalytic role of added protons are discussed.
Construction of Recombinant Escherichia coli Catalysts which Simultaneously Express an (S)‐Oxynitrilase and Different Nitrilase Variants for the Synthesis of (S)‐Mandelic Acid and (S)‐Mandelic Amide from Benzaldehyde and Cyanide
Authors: Sosedov Olga , Matzer Kathrin , Bürger Sibylle , Kiziak Christoph , Baum Stefanie , Altenbuchner Josef , Chmura Andrzej , van Rantwijk Fred , Stolz Andreas
Published: July 2009

Recombinant Escherichia coli strains were constructed which simultaneously expressed the genes encoding the (S)‐oxynitrilase from cassava (Manihot esculenta) together with the wild‐type or a mutant variant of the arylacetonitrilase from Pseudomonas fluorescens EBC191 in a single organism under the control of a rhamnose‐inducible promoter. The whole cell catalysts obtained converted benzaldehyde and potassium cyanide in aqueous media at pH 5.2 mainly to (S)‐mandelic acid and/or (S)‐mandelic amide and synthesized only low amounts of the corresponding (R)‐enantiomers. The conversion of benzaldehyde and potassium cyanide (KCN) by a whole‐cell catalyst simultaneously expressing the (S)‐oxynitrilase and the wild‐type nitrilase resulted in a ratio of (S)‐mandelic acid to (S)‐mandelic amide of about 4:3. This could be explained by the strong nitrile hydratase activity of the wild‐type nitrilase with (S)‐mandelonitrile as substrate. The relative proportion of (S)‐mandelic amide formed in this system was significantly increased by coexpressing the (S)‐oxynitrilase with a carboxy‐terminally truncated variant of the nitrilase. This whole‐cell catalyst converted benzaldehyde and KCN to mandelic amide and mandelic acid in a ratio of about 9:1. The ee of the (S)‐mandelic amide formed was calculated to be >95%.
Iron‐Catalyzed Ligand‐Free Carbon‐Selenium (or Tellurium) Coupling of Arylboronic Acids with Diselenides and Ditellurides
Authors: Wang Min , Ren Kai , Wang Lei
Published: July 2009

Carbon‐selenium and carbon‐tellurium cross‐couplings of arylboronic acids with diselenides and ditellurides have been catalyzed by iron(0), iron(II) chloride or iron(III) chloride without any ligand and additive in the air. The method yields the corresponding unsymmetrical diorgano monoselenides and monotellurides in good to excellent yields, displays a broad substrate scope, and is simple, convenient, effective, economical and environmentally friendly.
Selective Oxidation of Acetophenones Bearing Various Functional Groups to Benzoic Acid Derivatives with Molecular Oxygen
Authors: Nakamura Ryota , Obora Yasushi , Ishii Yasutaka
Published: July 2009

Acetophenones substituted by alkyl, alkoxy, acetoxy, and halogen groups were selectively oxidized with molecular oxygen to the corresponding benzoic acids by using the N,N′,N′′‐trihydroxyisocyanuric acid (THICA)/cobalt(II) acetate [Co(OAc)2] and THICA/Co(OAc)2/manganese(II) acetate [Mn(OAc)2]. For example, 4‐methylacetophenone was selectively oxidized with molecular oxygen to 4‐acetylbenzoic acid (85%) by THICA/Co(OAc)2 and to 4‐methylbenzoic acid (93%) by Mn(OAc)2, while terephthalic acid was obtained in 93% with the THICA/Co(OAc)2/Mn(OAc)2 catalytic system. It is interesting that the acetyl group on the aromatic ring is efficiently converted by a very small amount of Mn(OAc)2 to the corresponding carboxylic acid, and that the present method provides a versatile route to acetylbenzoic acids which are difficult to prepare by conventional methods.
Electrocatalytic Recycling of CO2 and Small Organic Molecules
Authors: Lee Jaeyoung , Kwon Youngkook , Machunda Revocatus L. , Lee Hye Jin
Published: July 2009

As global warming directly affects the ecosystems and humankind in the 21st century, attention and efforts are continuously being made to reduce the emission of greenhouse gases, especially carbon dioxide (CO2). In addition, there have been numerous efforts to electrochemically convert CO2 gas to small organic molecules (SOMs) and vice versa. Herein, we highlight recent advances made in the electrocatalytic recycling of CO2 and SOMs including (i) the overall trend of research activities made in this area, (ii) the relations between reduction conditions and products in the aqueous phase, (iii) the challenges in the use of gas diffusion electrodes for the continuous gas phase CO2 reduction, as well as (iv) the development of state of the art hybrid techniques for industrial applications. Perspectives geared to fully exploit the potential of zero‐gap cells for CO2 reduction in the gaseous phase and the high applicability on a large scale are also presented. We envision that the hybrid system for CO2 reduction supported by sustainable solar, wind, and geothermal energies and waste heat will provide a long term reduction of greenhouse gas emissions and will allow for continued use of the abundant fossil fuels by industries and/or power plants but with zero emissions.
Calixarene Dimers as Host Molecules for Biologically Important Di‐ and Oligophosphates
Authors: Zadmard Reza , Taghvaei‐Ganjali Saeed , Gorji Banafsheh , Schrader Thomas
Published: July 2009

A dimeric calixarene, with an aliphatic C6‐bridge and six anilinium head groups at its upper rim, preferably complexes diphosphates and oligonucleotides with more than 10 bonds between both anionic moieties. Free binding energies correlate with the length of the aliphatic bridge in a roughly linear fashion. The binding event, which is monitored by fluorescence titrations and competition experiments, relies on Coulomb interactions, as opposed to a nonpolar variant with tert‐butyl instead of ammonium groups; here, hydrophobic forces prevail, rendering the calixarene dimer selective for less polar cofactors such as FAD. The best guest for the hexaanilinium dimer is found in ssDNA, which carries multiple copies of the optimal trinucleotide for maximum attraction towards the extended cationic host. The recognition event is also observed in the environment of a lipid monolayer, and provides a means to quantify dimer diphosphate interactions by measuring p/A shifts.
Ester Hydrolysis by a Cyclodextrin Dimer Catalyst with a Tridentate N,N′,N′′‐Zinc Linking Group
Authors: Tang Si‐Ping , Zhou Ying‐Hua , Chen Huo‐Yan , Zhao Cun‐Yuan , Mao Zong‐Wan , Ji Liang‐Nian
Published: July 2009

A new β‐cyclodextrin dimer, 2,6‐dimethylpyridine‐bridged‐bis(6‐monoammonio‐β‐cyclodextrin) (pyridyl BisCD, L), is synthesized. Its zinc complex (ZnL) is prepared, characterized, and applied as a catalyst for diester hydrolysis. The formation constant (log KML=7.31±0.04) of the complex and deprotonation constant (pKa1=8.14±0.03, pKa2=9.24±0.01) of the coordinated water molecule were determined by a potentiometric pH titration at (25±0.1)°C, indicating a tridentate N,N′,N′′‐zinc coordination. Hydrolysis kinetics of carboxylic acid esters were determined with bis(4‐nitrophenyl)carbonate (BNPC) and 4‐nitrophenyl acetate (NA) as the substrates. The resulting hydrolysis rate constants show that ZnL has a very high rate of catalysis for BNPC hydrolysis, yielding an 8.98×103‐fold rate enhancement over uncatalyzed hydrolysis at pH 7.00, compared to only a 71.76‐fold rate enhancement for NA hydrolysis. Hydrolysis kinetics of phosphate esters catalyzed by ZnL are also investigated using bis(4‐nitrophenyl)phosphate (BNPP) and disodium 4‐nitrophenyl phosphate (NPP) as the substrates. The initial first‐order rate constant of catalytic hydrolysis for BNPP was 1.29×10−7 s−1 at pH 8.5, 35 °C and 0.1 mM catalyst concentration, about 1600‐fold acceleration over uncatalyzed hydrolysis. The pH dependence of the BNPP cleavage in aqueous buffer was shown as a sigmoidal curve with an inflection point around pH 8.25, which is nearly identical to the pKa value of the catalyst from the potentiometric titration. The kBNPP of BNPP hydrolysis promoted by ZnL is found to be 1.68×10−3 M−1 s−1, higher than that of NPP, and comparatively higher than those promoted by its other tridentate N,N′,N′′‐zinc analogues.
A simple and robust algorithm for microarray data clustering based on gene population‐variance ratio metric
Authors: Chatterjee Soumyadeep , Bhattacharjee Kasturi , Konar Amit
Published: July 2009

With the advent of the microarray technology, the field of life science has been greatly revolutionized, since this technique allows the simultaneous monitoring of the expression levels of thousands of genes in a particular organism. However, the statistical analysis of expression data has its own challenges, primarily because of the huge amount of data that is to be dealt with, and also because of the presence of noise, which is almost an inherent characteristic of microarray data. Clustering is one tool used to mine meaningful patterns from microarray data. In this paper, we present a novel method of clustering yeast microarray data, which is robust and yet simple to implement. It identifies the best clusters from a given dataset on the basis of the population of the clusters as well as the variance of the feature values of the members from the cluster‐center. It has been found to yield satisfactory results even in the presence of noisy data.
Characterisation of a Recombinant NADP‐Dependent Glycerol Dehydrogenase from Gluconobacter oxydans and its Application in the Production of L‐Glyceraldehyde
Authors: Richter Nina , Neumann Markus , Liese Andreas , Wohlgemuth Roland , Eggert Thorsten , Hummel Werner
Published: July 2009

The acetic acid bacterium Gluconobacter oxydans has a high potential for oxidoreductases with a variety of different catalytic abilities. One putative oxidoreductase gene codes for an enzyme with a high similarity to the NADP+‐dependent glycerol dehydrogenase (GlyDH) from Hypocrea jecorina. Due to this homology, the GlyDH (Gox1615) has been cloned, over‐expressed in Escherichia coli, purified and characterised. Gox1615 shows an apparent native molecular mass of 39 kDa, which corresponds well to the mass of 37.213 kDa calculated from the primary structure. From HPLC measurements, a monomeric structure can be deduced. Kinetic parameters and the dependence of the activity on temperature and pH were determined. The enzyme shows a broad substrate spectrum in the reduction of different aliphatic, branched and aromatic aldehydes. Additionally, the enzyme has been shown to oxidize a variety of different alcohols. The highest activities were observed for the conversion of D‐glyceraldehyde in the reductive and L‐arabitol in the oxidative direction. Since high enantioselectivities were observed for the reduction of glyceraldehyde, the kinetic resolution of glyceraldehyde was investigated and found to yield enantiopure L‐glyceraldehyde on preparative scale.
Magnetism in Nanoparticles: Beyond the Effect of Particle Size
Authors: Peddis Davide , Cannas Carla , Musinu Anna , Piccaluga Giorgio
Published: July 2009

A set of investigations on selected samples of nanosized cobalt ferrite are reviewed, aimed at studying the various factors affecting the magnetic properties of nanoparticles. Specifically, the effects of inter‐particle interactions, of structural and magnetic order, both in the core and on the surface of the particle, have been examined. All factors render the control of the magnetic properties of nanosystems quite difficult, but, at the same time, they also offer the opportunity of tuning them properly, so that materials for specific applications may be created.
New Mechanistic Aspects of the Fenton Reaction
Authors: Rachmilovich‐Calis Sandra , Masarwa Alexandra , Meyerstein Naomi , Meyerstein Dan , van Eldik Rudi
Published: July 2009

The kinetics of the Fenton reaction was studied in detail. A second reaction step in the presence of excess H2O2 is attributed to formation of the complex FeIII(−O2H)aq. Therefore, the reaction of Fe(H2O)62+ with FeIII(−O2H)aq in the presence of FeII to form FeIIIaq (k=(7.7±1.5)×105 M−1 s−1) may contribute to the overall Fenton reaction, and could account for some of the debate in the literature concerning its detailed mechanism. If this is correct for LFeIII(−O2H)aq also, then it might be of significant biological importance. The activation parameters ΔH≠, ΔS≠, and ΔV≠ for the Fenton reaction were measured under various experimental conditions, and are used in the mechanistic interpretation.
A Kinetic and Structural Investigation of DNA‐Based Asymmetric Catalysis Using First‐Generation Ligands
Authors: Rosati Fiora , Boersma Arnold J. , Klijn Jaap E. , Meetsma Auke , Feringa Ben L. , Roelfes Gerard
Published: July 2009

The recently developed concept of DNA‐based asymmetric catalysis involves the transfer of chirality from the DNA double helix in reactions using a noncovalently bound catalyst. To date, two generations of DNA‐based catalysts have been reported that differ in the design of the ligand for the metal. Herein we present a study of the first generation of DNA‐based catalysts, which contain ligands comprising a metal‐binding domain linked through a spacer to a 9‐aminoacridine moiety. Particular emphasis has been placed on determining the effect of DNA on the structure of the CuII complex and the catalyzed Diels–Alder reaction. The most important findings are that the role of DNA is limited to being a chiral scaffold; no rate acceleration was observed in the presence of DNA. Furthermore, the optimal DNA sequence for obtaining high enantioselectivities proved to contain alternating GC nucleotides. Finally, DNA has been shown to interact with the CuII complex to give a chiral structure. Comparison with the second generation of DNA‐based catalysts, which bear bipyridine‐type ligands, revealed marked differences, which are believed to be related to the DNA microenvironment in which the catalyst resides and where the reaction takes place.
Temperature‐Dependent Guest‐Driven Single‐Crystal‐to‐Single‐Crystal Ligand Exchange in a Two‐Fold Interpenetrated CdII Grid Network
Authors: Zhuang Chun‐Feng , Zhang Jianyong , Wang Qing , Chu Zhao‐Hua , Fenske Dieter , Su Cheng‐Yong
Published: July 2009

A doubly interpenetrated square‐grid coordination polymer {[Cd(ImBNN)2(CF3SO3)2]⊃guest}n (1) (guest=C7H8 and ImBNN=2,5‐bis[4′‐(imidazol‐1‐yl)phenyl]‐3,4‐diaza‐2,4‐hexadiene) that contains cavities able to accommodate toluene guest molecules has been assembled by the reaction of the Schiff base ligand ImBNN and Cd(CF3SO3)2. The framework 1 shows dynamism in either temperature‐dependent expansion and shrinkage or cooperatively temperature‐dependent guest‐driven ligand exchange at the metal center. Studies of guest removal/uptake by heating in a vacuum, cooling in air, and then heating in toluene at reflux have revealed a series of single‐crystal‐to‐single‐crystal structural transformations: complex 1 lost toluene guests and captured water molecules to give guest‐free 1 b via a proposed metastable phase 1 a, and 1 b could readsorb toluene guests to give 1′, which represents a restored 1. These structural changes establish an indirect recoverable process that involves ligand exchange in the coordination sphere and guest exchange in the cavity accompanied by the cleavage/formation of CdO bonds and CF3SO3− anion‐shifting. In contrast, direct heating of 1 in the absence of a vacuum resulted in thermostable 1 c, confirmed by X‐ray powder diffraction as a new phase that could not be converted back into 1 and that had lost the ability of readsorbing toluene guests.
Biomolecule‐Functionalized Nanowires: From Nanosensors to Nanocarriers
Authors: Wang Joseph
Published: July 2009

The unique properties of nanowires offer excellent prospects for designing a new generation of devices and systems exhibiting novel functions. This Review discusses recent scientific accomplishments in the preparation of nanowire–biomaterial hybrids and their potential applications as nanosensors, nanoactuators, and nanocarriers. Nanowires can be readily functionalized with various biochemicals through different linkage chemistries. Such integration of nanowires and biomolecules leads to novel hybrid systems which couple the recognition or catalytic properties of biomaterials with the attractive electronic and structural characteristics of nanowires. Receptor‐functionalized nanowires are particularly attractive for direct real‐time label‐free electrical detection of biomolecular interactions. The unique control over the microstructure of nanowires, and particularly the design of multisegment nanowires, offer spatially defined regions for the defined organization of different biomolecules. This allows the resulting nanowires to perform several tasks simultaneously, and opens the door to a variety of important applications in the areas of nanobioelectronics and nanomedicine. For example, multisegment nanowires designed for nanomedicine applications can couple the selective targeting, therapy, and imaging functions. Such spatially defined anchoring of different biorecognition sites provides also distinct opportunities for the self assembly of nanowires into predetermined designs. The opportunities and challenges involved in designing such nanowire–biomaterial hybrid systems and devices are discussed in the following sections.
Shaping corporate environmental performance: a review
Authors: Gunningham Neil
Published: July 2009

The aims of this review article are to map the development of the corporate environmental responsibility (CER) concept, to trace the principal debates concerning its contribution to environmental protection, to examine the arguments about the relationship between CER and competitive advantage and to examine whether, to what extent and in what circumstances business behaviour is shaped by broader external forces, not least by markets, governments and civil society. From here, the article concludes by drawing some explicit implications for environmental policy and governance. Copyright © 2009 John Wiley & Sons, Ltd and ERP Environment.
Polymer‐Derived SiOC Nanotubes and Nanorods via a Template Approach
Authors: Pashchanka Mikhail , Engstler Jörg , Schneider Jörg J. , Siozios Vassilios , Fasel Claudia , Hauser Ralf , Kinski Isabel , Riedel Ralf , Lauterbach Stefan , Kleebe Hans‐Joachim , Flege Stefan , Ensinger Wolfgang
Published: July 2009

The synthesis of silicon‐based ceramic nanowires and nanotubes produced by liquid infiltration of commercially available silicon‐based polymers, namely polysilazane (CerasetTM, polyureasilazane), polysilazane VL20 (Kion Coop.) and polycarbosilane (Starfire Systems SP‐MatrixTM) in alumina templates with defined pore channels is reported. After polymer infiltration, pyrolysis of the preceramic polymer at 1000–1100 °C in Ar atmosphere followed by dissolution of the alumina templates, ceramic nanowires and nanotubes were obtained. In the case of the polymeric ceramic precursor polysilazane, nanorods were formed only if an oligomeric fraction was distilled off from the polymer precursor prior to infiltration of the template. In contrast, the formation of nanotubes was found after infiltration of the untreated (crude) preceramic polymer. Despite the fact that the preceramic polymers contain silicon, carbon and nitrogen and no oxygen as constituting elements, the final ceramic nanostructures obtained were analysed consistantly by various techniques to contain oxygen and only limited amounts of carbon and nitrogen after pyrolysis consistent with a composition as silicon oxycarbide (SiOC). This behaviour strongly indicates that the porous alumina template may significantly influence the pyrolysis process of the precursors thus affecting the chemical composition of the final ceramic products. It is a central result of our study that the alumina templates are not inert under the reaction conditions employed instead acting as a reaction partner at the high temperatures employed during pyrolysis. Taking this into account, reaction of otherwise inert amorphous alumina with inorganic polymers at elevated temperatures could lead to a directed synthesis of new ceramic compositions.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
The influence of mastery‐avoidance goals on performance improvement
Authors: Van Yperen Nico W. , Elliot Andrew J. , Anseel Frederik
Published: July 2009

Two experiments focused on examining the influence of mastery‐avoidance goals on performance improvement, and more specifically, on mastery‐avoidance goals grounded in an intrapersonal standard. That is, herein, mastery‐avoidance goals entail striving to avoid doing worse than one has done before. Both experiments demonstrated that in a multiple‐trial context, mastery‐avoidance goals are deleterious for performance improvement relative to mastery‐approach, performance‐approach, and performance‐avoidance goals, and a no goal baseline. The findings were shown to be independent of participants' perceptions of goal difficulty, and were consistent not only across methodology but also across type of participant (undergraduates versus individuals in the workforce), and type and length of achievement task (a verbal skills task versus an ecologically valid managerial competencies exercise). Copyright © 2009 John Wiley & Sons, Ltd.
Retracted: Judging the unexpected: Disconfirmation of situation‐specific expectancies
Authors: Noordewier Marret K. , Stapel Diederik A.
Published: July 2009

People's interactions with others typically take place in specific situations. Therefore, it is likely that expectancies of others are often situation‐specific. In two studies, we examined when and how this situation‐specificity of expectancies affects judgment.We showed that situation‐specific expectancies ‘“Michael is kind at work”’ lead to surprise and contrast effects when incongruent behavior refers to the same specific situation ‘work’, but not in other situations ‘general or home’, whereas general expectancies ‘“Michael is kind”’ lead to such surprise and contrast effects, regardless of the target situation. These results suggest that people sometimes are “situationalists” and do not always show dispositional biases. Copyright © 2009 John Wiley & Sons, Ltd.
Nonlinear locally weighted kriging prediction for spatio‐temporal environmental processes
Authors: Bodnar Olha , Schmid Wolfgang
Published: July 2009

In the paper, a nonlinear interpolation procedure for the spatial prediction of an environmental process is proposed. The suggested interpolation is based on the locally weighted scatterplot smoothing method of Cleveland in 1979. This approach is applied to a nonlinear spatio‐temporal model. In an empirical study, the PM10 concentration in the Berlin—Brandenburg region of Germany is considered. It is shown that the local approach permits a more structured interpolation of the air pollution. Copyright © 2009 John Wiley & Sons, Ltd.
Synthesis of 2H‐ and 13C‐labelled sunitinib and its primary metabolite
Authors: Elsinghorst Paul W. , Gütschow Michael
Published: July 2009

Sunitinib (Sutent®, Pfizer) was approved in 2006 for the treatment of gastrointestinal and renal cancer. Isotope‐labelled derivatives have already been prepared for PET and ADME radiography. The preparation of 13C‐ and 2H‐labelled internal standards of sunitinib (SU11248) and its primary metabolite (SU12662) for LC‐MS analysis of human blood samples is presented. Copyright © 2009 John Wiley & Sons, Ltd.
Synthesis of carbon‐14 labelled midazolam
Authors: Easter John A. , Burrell Richard C. , Bonacorsi Samuel J. , Balasubramanian Balu
Published: July 2009

Cytochrome P450 (CYP) enzymes are responsible for much of the phase I oxidative metabolism observed in vivo. Many important pharmaceutical compounds are metabolized by CYP. Co‐administration of a drug with another agent can alter the efficacy or the toxicity, especially in cases where drug clearance depends primarily on the CYP metabolism. Compounds that induce or inhibit the CYP activity are often used in drug–drug interaction studies. Midazolam is one such compound that is routinely used in drug–drug interaction studies because it is a known substrate for CYP3A enzymes. The synthesis of this important tool molecule has been documented, but unfortunately a detailed preparation of carbon‐14‐labelled midazolam has not been reported in the literature. This paper describes a two‐step synthesis leading to [14C]midazolam. A total of 4.5 mCi of [14C]midazolam was obtained having a specific activity of 120.1 µCi/mg (39.12 mCi/mmol). The radiochemical purity as determined by HPLC was 99.8% and the overall radiochemical yield was 9%. Copyright © 2009 John Wiley & Sons, Ltd.
Novel and efficient detection of cAMP‐dependent protein kinase for the development of a protein biochip
Authors: Park Sang Hyun , Ko Kyong‐Cheol , Choi Mi Hee
Published: July 2009

Protein microarrays have recently become a powerful research tool for proteomics and clinical investigations. A novel and efficient detection of cAMP‐dependent protein kinase for the development of a protein biochip has been established. The phosphorylation of a substrate by [γ‐33P]ATP and [γ‐32P]ATP was performed on a glass chip, and a facile detection of a kinase assay using 32P and 33P on a glass chip was accomplished by a radio‐TLC imaging scanner. Since the radio‐TLC detection method takes shorter detection time (2 min) than those required for X‐ray film or bioimage analyzer (6–12 h), the latter can be replaced. The detection by the radio‐TLC was proven to be rapid and suitable for a kinase assay using radioisotopes for developing a biochip. Copyright © 2009 John Wiley & Sons, Ltd.
Periodic knee injections of BMP‐7 delay cartilage degeneration induced by excessive running in rats
Authors: Sekiya Ichiro , Tang Tao , Hayashi Masaya , Morito Toshiyuki , Ju Young‐Jin , Mochizuki Tomoyuki , Muneta Takeshi
Published: July 2009

Strenuous running of rats enhances mechanical stress on the knee, thereby inducing degeneration of articular cartilage. Bone morphogenetic protein‐7 (BMP‐7) has an inhibitory effect on cartilage degeneration, suggesting its usefulness for human osteoarthritis patients. However, its mode of administration should be investigated. We examined whether weekly knee injections of BMP‐7 delayed the progression of cartilage degeneration. Wistar rats were forced to run 30 km in 6 weeks on a rodent treadmill, and BMP‐7 was injected weekly into the knee. Macroscopically and histologically, this strenuous running regimen induced cartilage degeneration. Weekly injections of 250 ng BMP‐7 delayed the progression of cartilage degeneration. Immunohistochemically, in the control knee, type II collagen expression decreased, while BMP‐7 expression in chondrocytes slightly increased. Interestingly, weekly injection of BMP‐7 increased BMP‐7 expression even 9 days after the final injection. Disulfate disaccharide keratan sulfate in serum transiently increased in the control group, while it remained at a low level in the BMP‐7 group. Weekly BMP‐7 injection increased BMP‐7 expression in chondrocytes and its effect seemed to last more than 7 days. The effect of BMP‐7 could be monitored by serum keratan sulfate concentration. Periodical injections of BMP‐7 delayed progression of cartilage degeneration induced by excessive running in rats. © 2009 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 27: 1088–1092, 2009
Cropping strategies, soil fertility investment and land management practices by smallholder farmers in communal and resettlement areas in Zimbabwe
Authors: Cobo J. G. , Dercon G. , Monje C. , Mahembe P. , Gotosa T. , Nyamangara J. , Delve R. J. , Cadisch G.
Published: July 2009

Three smallholder villages located in typical communal (from 1948), old (1987) and new (2002) resettlement areas, on loamy sand, sandy loam and clay soils, respectively, were selected to explore differences on natural resource management and land productivity. Focus group discussions and surveys were carried out with farmers. Additionally, farmers in three wealth classes per village were chosen for a detailed assessment of their main production systems. Maize grain yields (t ha−1) in the communal (1·5–4·0) and new resettlement areas (1·9–4·3) were similar but significantly higher than in the old resettlement area (0·9–2·7), despite lower soil quality in the communal area. Nutrient input use was the main factor controlling maize productivity in the three areas (R2 = 59–83%), while soil quality accounted for up to 12%. Partial N balances (kg ha−1 yr−1) were significantly lower in the new resettlement (−9·1 to +14·3) and old resettlement (+7·4 to +9·6) than in the communal area (+2·1 to +59·6) due to lower nutrient applications. Averaged P balances were usually negative. Consistently, maize yields, nutrient applications and partial N balances were higher in the high wealth class than in poorer classes. This study found that most farmers in the new resettlement area were exploiting the inherent soil nutrient stocks more than farmers in the other two areas. We argue that effective policies supporting an efficient fertilizer distribution and improved soil management practices, with clearer rights to land, are necessary to avoid future land degradation and to improve food security in Zimbabwe, particularly in the resettlement areas. Copyright © 2009 John Wiley & Sons, Ltd.
Semiconductor Dendritic‐Linear Block Copolymers by Nitroxide Mediated Radical Polymerization
Authors: Lang Andreas S. , Kogler Franz René , Sommer Michael , Wiesner Ulrich , Thelakkat Mukundan
Published: July 2009

The first synthesis of a semiconductor hybrid diblock copolymer comprised of p‐type dendritic and n‐type linear blocks by nitroxide mediated radical polymerization (NMRP) is reported. A triphenylamine (TPA) bearing second generation polyether dendron [G2]‐OH has been functionalized with an alkoxyamine and, subsequently, perylene bisimide acrylate (PerAcr) was polymerized to obtain a hybrid block copolymer, [G2]‐b‐PPerAcr. The hybrid block copolymer structure is supported by 1H NMR and size exclusion chromatography. Furthermore, the novel materials were studied by UV‐vis absorption spectrometry, photoluminescence, cyclic voltammetry, differential scanning calorimetry and thermogravimetry analysis.

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Gestärkt aus der Krise — Worthülse oder Perspektive?
Authors: Jung Udo
Published: July 2009

Der wirtschaftliche Zustand in einzelnen Regionen und Abnehmerindustrien wirkt auf die Produktsegmente der chemischen Industrie unterschiedlich. Vorteile haben Unternehmen, die sich von schwachen Geschäften trennen und starke unterstützen können.
Investieren für die Zeit nach dem Öl
Authors: Osterath Brigitte
Published: July 2009

Ihr Öl hat sie reich gemacht. Doch was, wenn die Ölquellen versiegen? Die erdölproduzierenden Staaten am persischen Golf investieren inzwischen vermehrt in die Forschung und suchen Unterstützung bei international renommierten Universitäten. Auch deutsche Hochschulen sind gefragt.
Wem gehört die Erfindung — Kooperationsverträge
Authors: Schneier Michael
Published: July 2009

Forschungs‐ und Entwicklungsprojekte, insbesondere in Bereichen wie Bio‐ oder Nanotechnologie, erfordern die Zusammenarbeit von Forschern aus Industrie und Hochschulen. Synergien werden staatlich gefördert. Allerdings sind die institutionellen Rahmenbedingungen, Organisationsformen und Wertvorstellungen von Industrieunternehmen und Hochschulen unterschiedlich. Den jeweiligen Interessen sollen Kooperationsverträge Rechnung tragen.
Non‐Hodgkin lymphoma following temozolomide
Authors: Sharma Atul , Gupta Deepak , Mohanti B.K. , Thulkar Sanjay , Dwary Amit , Goyal Shikha , Muzumder Sandeep , Das Prasenjit
Published: July 2009

Temozolomide (TMZ) is an oral alkylating agent with significant activity against glioblastoma multiforme (GBM) and melanoma. It increases survival by 2.5 months when used in combination with radiotherapy as an adjuvant therapy in GBM. Secondary MDS/AML or non‐Hodgkin lymphoma attributed to TMZ exposure has been reported. We report a case of non‐Hodgkin lymphoma secondary to temozolomide in a 20‐year‐old female who was treated for GBM with concurrent TMZ and radiotherapy. She developed lymphoma 2 months after completing chemoradiotherapy. Although she was treated with combination chemotherapy for lymphoma, she died of progressive GBM. Pediatr Blood Cancer 2009;53:661–662. © 2009 Wiley‐Liss, Inc.
Nutritional problems in children treated for medulloblastoma: Implications for enteral nutrition support
Authors: Ward Evelyn , Hopkins Monica , Arbuckle Lesley , Williams Nicola , Forsythe Lynette , Bujkiewicz Sylwia , Pizer Barry , Estlin Edward , Picton Susan
Published: July 2009

Background

The aim of this study was to identify the nature and severity of nutritional problems associated with the current treatment of medulloblastoma and to identify any risk factors for nutritional morbidity during treatment.

Procedure

A multicentre retrospective audit of medical and dietetic notes of 41 children treated for medulloblastoma in three UK paediatric oncology centres was undertaken. Data on nutritional status, nutritional support, mutism, swallowing and common toxicity criteria (CTC) scores for vomiting, constipation and mobility were collected at defined points in treatment from diagnosis until 12 months post‐treatment.

Results

Significant problems including weight loss, vomiting and constipation were highlighted early on in treatment. The majority of patients were well nourished at diagnosis with a mean percentage weight: height of 99.8%, however nutritional status started to decline early in treatment during radiotherapy, coinciding with 49% of patients having grade 1 or above CTC score for vomiting and constipation. The decline in nutritional status continued, peaking by course 2 of chemotherapy with a mean weight loss of 8.2% since diagnosis. Proactive supplementary feeding early in treatment by one of the three centres demonstrated a superior nutritional outcome when compared statistically to the two centres that fed only as a response to nutritional decline.

Conclusion

The study highlighted significant morbidity associated with the current treatment of medulloblastoma. Findings suggest the need to consider earlier proactive nutritional intervention to prevent nutritional decline during treatment. These early nutritional problems may be related to toxicities of radiotherapy and concomitant vincristine. Pediatr Blood Cancer 2009;53:570–575. © 2009 Wiley‐Liss, Inc.
Thrombotic thrombocytopenic purpura in childhood
Authors: Bouw Maria C. , Dors Natasja , van Ommen Heleen , Ramakers‐van Woerden Nicole L.
Published: July 2009

Thrombotic thrombocytopenic purpura (TTP) is a rare disease, especially in childhood, and has a high mortality rate in the absence of appropriate treatment. It is characterised by microangiopathic haemolytic anaemia and consumptive thrombocytopenia. TTP may be difficult to distinguish from haemolytic uraemic syndrome (HUS) because of similar clinical manifestations and laboratory findings. In the past, TTP and HUS have often been considered to represent variable expressions of a single entity. Our increased understanding of the pathogenesis of TTP has in turn resulted in significant improvements in its treatment and outcomes. Several immunomodulating agents are currently being used with variable outcomes. Pediatr Blood Cancer 2009;53:537–542. © 2009 Wiley‐Liss, Inc.
Differences in activities of daily living performance between long‐term pediatric sarcoma survivors and a matched comparison group on standardized testing
Authors: Parks Rebecca , Rasch Elizabeth K. , Mansky Patrick J. , Oakley Frances
Published: July 2009

Background

In a cross‐sectional study examining late effects of pediatric sarcoma therapy, long‐term survivors were evaluated on their activities of daily living (ADL) performance.

Procedure

Thirty‐two persons with Ewing sarcoma family of tumors, rhabdomyosarcoma, and non‐rhabdomysarcoma‐soft tissue sarcoma enrolled an average of 17 years after treatment. Participants were evaluated using the Assessment of Motor and Process Skills (AMPS) 1, a standardized observational evaluation of ADL task performance. Means and 95% confidence intervals for ADL motor and ADL process ability measures were calculated for four groups: (1) sarcoma survivors, (2) “well” adults matched for age and gender, (3) “well” adults matched for gender that were 10 years older, and (4) “well” adults matched for gender that were 20 years older.

Results

ADL motor ability was significantly lower for sarcoma survivors than for the age‐ and gender‐matched comparison group (P < 0.05). There was no significant difference between ADL motor ability of sarcoma survivors and the comparison group 10 years older, but sarcoma survivors had significantly better ADL motor ability (P < 0.05) than the oldest comparison group (20 years older). Sarcoma survivors had significantly worse ADL process ability than the age‐matched group (P < 0.05). There was no difference in ADL process ability between the sarcoma survivors and comparison groups that were 10 and 20 years older.

Conclusions

This first report of a clinical evaluation of ADL limitation in pediatric sarcoma survivors treated with intensive multimodal cancer therapy suggests that influences on performance of daily life activities are more common than previously reported. Pediatr Blood Cancer 2009;53:622–628. Published 2009 Wiley‐Liss, Inc.
Prevalence of abnormal bone density of pediatric patients prior to blood or marrow transplant
Authors: Klopfenstein Kathryn J. , Clayton Julie , Rosselet Robin , Kerlin Bryce , Termuhlen Amanda , Gross Thomas
Published: July 2009

Osteoporosis and osteopenia are long‐term side effects of bone marrow transplant (BMT). The purpose of this study was to determine the prevalence of bone mineral density (BMD) abnormalities in pediatric patients prior to BMT. Forty‐four pediatric patients were evaluated with DEXA scans. The average Z‐score was −0.37. Thirty‐six percent had abnormal BMD. Sixty‐seven percent of ALL patients had abnormal BMD. Patients with non‐malignant diseases were significantly more likely to have abnormal BMD. Patients with ALL had more defects than solid tumor patients. Females had more defects than males. These results demonstrate BMD defects are common in children prior to BMT, especially in patients with ALL. Pediatr Blood Cancer 2009;53:675–677. © 2009 Wiley‐Liss, Inc.
Clinicopathological characteristics of ganglioneuroma and ganglioneuroblastoma: A report from the CCG and COG
Authors: Okamatsu Chizuko , London Wendy B. , Naranjo Arlene , Hogarty Michael D. , Gastier‐Foster Julie M. , Look A. Thomas , LaQuaglia Michael , Maris John M. , Cohn Susan L. , Matthay Katherine K. , Seeger Robert C. , Saji Tsutomu , Shimada Hiroyuki
Published: July 2009

Background

The International Neuroblastoma Pathology Classification (INPC) was the first to clearly define prognostic subgroups in ganglioneuroma (GN) and ganglioneuroblastoma (GNB).

Procedure

Histopathology and tumor resectability of 552 GN/GNB cases from the Children's Cancer Group (CCG) and Children's Oncology Group (COG) neuroblastoma studies were reviewed. The results were analyzed along with clinical information and biological data of the cases.

Results

According to the INPC, 300 tumors were classified into the Favorable Histology (FH) group and 252 were into the Unfavorable Histology (UH) group. Tumors in the FH group included 43 ganglioneuroma‐maturing (GN‐M), 198 ganglioneuroblastoma‐intermixed (GNB‐I), and 59 ganglioneuroblastoma‐nodular, favorable subset (GNB‐N‐FS), and were often (91%) resected completely by single or multiple surgical procedures. Patients with the FH tumors had an excellent prognosis with no tumor‐related deaths. The UH group included ganglioneuroblastoma‐nodular, unfavorable subset (GNB‐N‐US) tumors. Patients with the UH tumors had a high incidence (53%) of distant metastasis at the time of diagnosis, and their prognosis significantly depended on clinical stage (5‐year EFS: 80.1% for non‐stage 4 patients; 16.7% for stage 4 patients): Complete primary tumor resection was not beneficial to those GNB‐N‐US patients, regardless of whether metastasis was present or not. MYCN amplification was detected in four tumors in the FH group and six tumors in the UH group. The majority (160/191, 84%) of GN‐M and GNB‐I tumors had a diploid pattern determined by flow cytometry.

Conclusions

Stringent application of the INPC along with clinical staging was critical for prognostic evaluation of the patients with this group of tumors. Pediatr Blood Cancer 2009;53:563–569. © 2009 Wiley‐Liss, Inc.