bluuebunny/crossref_metadata_2025 huggingface dataset:
Titelbild: Ein substituentenfreier Galliumligand durch Hydrogenolyse von koordiniertem GaCp*: Synthese und Struktur des hoch fluktionalen [Ru2(Ga)(GaCp*)7(H)3] (Angew. Chem. 21/2009)
Authors: Cadenbach Thomas , Gemel Christian , Schmid Rochus , Halbherr Markus , Yusenko Kirill , Cokoja Mirza , Fischer Roland A.
Published: May 2009

Weiche Schale, harter Kern ist das Grundprinzip für die Bildung einer Nanolegierung aus molekularen Vorstufen. Die gemeinsame Hydrogenolyse von Rutheniumkomplexen in Gegenwart von GaCp* führt zum isolierbaren Schlüsselintermediat [Ru2(Ga)(GaCp*)7 (H)3] mit einem substituentenfreien Gallium‐Brückenatom. Aus dieser “embryonalen” Spezies bilden sich unter vollständiger Abspaltung der Cp*‐Schutzhülle (im Bild als Eierschale dargestellt) Ru‐Ga‐Phasen, wie R. A. Fischer et al. in ihrer Zuschrift auf S. 3930 ff. beschreiben.

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Innentitelbild: Giant Pores in a Chromium 2,6‐Naphthalenedicarboxylate Open‐Framework Structure with MIL‐101 Topology (Angew. Chem. 21/2009)
Authors: Sonnauer Andreas , Hoffmann Frank , Fröba Michael , Kienle Lorenz , Duppel Viola , Thommes Matthias , Serre Christian , Férey Gérard , Stock Norbert
Published: May 2009

Hoch poröse und stabile kristalline Gerüstverbindungen wurden unter Zuhilfenahme von Hochdurchsatzmethoden hergestellt, wie N. Stock et al. in ihrer Zuschrift auf S. 3849 ff. berichten. Eine zu MIL‐101 isoretikuläre Verbindung mit Zeolith‐analoger MTN‐Topologie und Käfigen mit 39 und 46 Å Durchmesser wurde durch Verwendung von 2,6‐Naphthalindicarbonsäure erhalten und konnte anhand von Struktursimulationen sowie elektronenmikroskopischen Daten und Sorptionsmessungen charakterisiert werden.

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Total Synthesis and Stereochemical Assignment of Micrococcin P1
Authors: Lefranc David , Ciufolini Marco A.
Published: April 2009

Fifty years after the discovery of the thiopeptide antibiotic micrococcin P1, the constitutional and stereochemical uncertainties concerning its structure have been lifted with its total synthesis and absolute stereochemical assignment (see picture).

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Linear π‐Acceptor‐Templated Dynamic Clipping to Macrobicycles and [2]Rotaxanes
Authors: Klivansky Liana M. , Koshkakaryan Gayane , Cao Dennis , Liu Yi
Published: April 2009

Cage me! A linear dumbbell‐shaped bipyridinium molecule can template cage formation around itself through sixfold imine bond formation to give an interlocked [2]rotaxane as the single product (see picture). This highly efficient [2+3] clipping occurs despite the symmetry mismatch between the template and the formed macrobicycle.

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Spontaneous Formation of Giant Unilamellar Vesicles from Microdroplets of a Polyion Complex by Thermally Induced Phase Separation
Authors: Oana Hidehiro , Kishimura Akihiro , Yonehara Kei , Yamasaki Yuichi , Washizu Masao , Kataoka Kazunori
Published: April 2009

Water pump: Polyion complex (PIC) vesicles are spontaneously formed from PIC microdroplets, which are formed by mixing cationic and anionic polymers (see picture). The formation process can be reversibly controlled by local heating with a focused infrared laser that triggers microphase separation and subsequent water influx. The size of the resulting giant unilamellar vesicles is determined by the initial size of the PIC droplets.

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The Monoammoniate of Lithium Borohydride, Li(NH3)BH4: An Effective Ammonia Storage Compound
Authors: Johnson Simon R. , David William I. F. , Royse David M. , Sommariva Marco , Tang Christina Y. , Fabbiani Francesca P. A. , Jones Martin O. , Edwards Peter P.
Published: April 2009

Store it up: The ammoniate, Li(NH3)BH4, has been prepared and fully characterized by Raman and NMR spectroscopy and X‐ray powder diffraction. The potential for its use as an ammonia store and a comparison to other ammonia storage materials is discussed.

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Lithium borohydride absorbs anhydrous ammonia to form four stable ammoniates; Li(NH3)nBH4, mono‐, di‐, tri‐, and tertraammoniate. This paper focuses on the monoammoniate, Li(NH3)BH4, which is readily formed on exposure of LiBH4 to ammonia at room temperature and pressure. Ammonia loss from Li(NH3)BH4 commences around 40 °C and the compound transforms directly to LiBH4. The crystal structure of Li(NH3)BH4 is reported here for the first time. Its close structural relationship with LiBH4 provides a clear insight into the facile nature and mechanism of ammonia uptake and loss. These materials not only represent an excellent high weight‐percent ammonia system but are also potentially important hydrogen stores.
It's a long way from amphioxus: descendants of the earliest chordate
Authors: Garcia‐Fernàndez Jordi , Benito‐Gutiérrez Èlia
Published: April 2009

The origin of chordates and the consequent genesis of vertebrates were major events in natural history. The amphioxus (lancelet) is now recognised as the closest extant relative to the stem chordate and is the only living invertebrate that retains a vertebrate‐like development and body plan through its lifespan, despite more than 500 million years of independent evolution from the stem vertebrate. The inspiring data coming from its recently sequenced genome confirms that amphioxus has a prototypical chordate genome with respect to gene content and structure, and even chromosomal organisation. Pushed by joint efforts of amphioxus researchers, amphioxus is now entering a new era, namely its maturation as a laboratory model, through the availability of a large amount of molecular data and the advent of experimental manipulation of the embryo. These two facts may well serve to illuminate the hidden secrets of the genetic changes that generated, among other vertebrates, ourselves.
Epidemiology of a tick‐borne viral infection: theoretical insights and practical implications for public health
Authors: Moshkin Mikhail P. , Novikov Eugene A. , Tkachev Sergey E. , Vlasov Valentin V.
Published: April 2009

The morbidity of tick‐borne encephalitis (TBE) varies yearly by as much as 10‐fold among the people of Western Siberia. This long‐term variation is dependent on many factors such as the density of the tick populations, the prevalence of TBE virus (TBEV) among sub‐adult ticks, the yearly virulence of the TBEV, and prophylactic measures. Here we highlight the role of small mammal hosts in the circulation of TBEV through the ecosystem. Refining classical models of non‐viremic horizontal transmission, we emphasize the recently understood fact that the physiological and immunological status of the small mammal hosts affects the tick and virus‐host interactions. In addition to its theoretical interest, our approach may lead to some practical improvements in the precision of epidemiological forecasts and perhaps in forestalling the severity of outbreaks of TBE, or, at least, in forewarning medical authorities and the general public of impending TBE outbreaks.
Thermodynamic and Computational Studies on the Binding of p53‐Derived Peptides and Peptidomimetic Inhibitors to HDM2
Authors: Grässlin Anja , Amoreira Celine , Baldridge Kim K. , Robinson John A.
Published: April 2009

Helix power: The binding interactions of linear and constrained β‐hairpin‐shaped peptides with HDM2 were compared by using experimental and theoretical methods. The entropic advantages enjoyed by the constrained peptides were found to be largely offset by reduced enthalpic contributions to binding of the cyclic mimetics. Formation of hydrogen bonds upon helix folding could contribute significantly to the enhanced enthalpy observed in binding of the linear peptides.

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The human double minute 2 protein (HDM2) binds a short peptide derived from the N terminus of the tumor‐suppressor protein, p53. This peptide (p53 residues 15–29) is flexible in free solution, but upon binding to HDM2 it folds into an amphipathic α‐helical conformation. Three residues along one face of the p53 helix (Phe19, Trp23, and Leu26) dock into hydrophobic pockets on the surface of HDM2. A conformationally constrained cyclic β‐hairpin peptidomimetic of p53, with residues Phe1, 6‐chloro‐Trp3, and Leu4 in one strand of the β‐hairpin, was shown earlier to dock into the same pockets on HDM2. Here, we show by isothermal titration calorimetry that the entropy loss upon binding of the constrained peptide to HDM2 is, as would be expected, much lower (TΔS≈10 kcal mol−1 at 300 K) than that for the linear peptide. However, the entropic advantage enjoyed by the constrained peptide is largely offset by a reduced enthalpic contribution, relative to the linear peptide, to binding of the cyclic mimetic. To explore the electronic nature of the interactions between the energetically important residues in each ligand and HDM2, hybrid quantum mechanical and electrostatic Poisson–Boltzmann computational studies were performed. The calculations reveal that significant stabilizing van der Waals interactions and polarization effects occur between the Trp side chain in each ligand and aromatic and aliphatic residues in HDM2. These stabilizing interactions are enhanced when a 6‐chloro substituent is incorporated into the Trp, in agreement with the experimental studies. In addition, the calculations suggest that at least one stabilizing hydrogen bond is formed, between the Trp indole‐NH in both ligands and HDM2. Other hydrogen‐bonding interactions also arise, however, along the α‐helical backbone of the linear peptide upon binding to HDM2, but are not mimicked in the constrained inhibitor–HDM2 complex. The formation of these hydrogen bonds upon helix folding could contribute significantly to the enhanced enthalpy observed in binding of the linear peptide to HDM2.
Warped factor analysis
Authors: Hong Sungjin
Published: April 2009

Shifted factor analysis (SFA) is designed to fit overall position shifts of sequential factors as well as the variation of factor weights. SFA is one kind of nonlinear generalization of linear factor models such as the two‐mode principal component model and the three‐mode Parafac model. Warped factor analysis (WFA), presented here, further generalizes SFA so that it fits factor variation due to not only the position shifts and the systematic weighting but also more flexible shape changes of sequential factors. A quasi alternating least squares (ALS) procedure is developed for WFA, using a simplified warping of segmented sequential factors. The most unique property of WFA is that it allows sequential factors to change shape distinctively, which is unlike what is implicitly assumed in mapping of data profiles, namely that sequential factors change shape together. Unlike the two‐mode factor/component models, two‐mode SFA was empirically shown to yield an essentially unique solution, using the additional sources of information provided by fitting systematic position shifts. Likewise, factors recovered by two‐mode WFA are likely to be essentially unique due to the systematic shape variance fit by the model, provided that the data contain sufficient sources of shape variation. Copyright © 2009 John Wiley & Sons, Ltd.
Robustified least squares support vector classification
Authors: Debruyne Michiel , Serneels Sven , Verdonck Tim
Published: April 2009

Support vector machine (SVM) algorithms are a popular class of techniques to perform classification. However, outliers in the data can result in bad global misclassification percentages. In this paper, we propose a method to identify such outliers in the SVM framework. A specific robust classification algorithm is proposed adjusting the least squares SVM (LS‐SVM). This yields better classification performance for heavily tailed data and data containing outliers. Copyright © 2009 John Wiley & Sons, Ltd.
Rearrangement of β‐amino alcohols and application to the synthesis of biologically active compounds
Authors: Cossy Janine , Pardo Domingo Gomez , Dumas Cécile , Mirguet Olivier , Déchamps Ingrid , Métro Thomas‐Xavier , Burger Benjamin , Roudeau Rémi , Appenzeller Jérôme , Cochi Anne
Published: April 2009

β‐Amino alcohols derived from natural amino acids have been used extensively as a powerful source of chirality. Transformation of the hydroxy group of these β‐amino alcohols into a good leaving group, by using trifluoroacetic anhydride, led to rearranged β‐amino alcohols in good yields and with high enantiomeric excesses. This rearrangement has allowed the transformation of substituted prolinols to substituted 3‐hydroxypiperidines and linear β‐amino alcohols, issued from natural amino acids, to rearranged β‐amino alcohols. Chirality, 2009. © 2009 Wiley‐Liss, Inc.
Chiral amino amides for the ruthenium(II)‐catalyzed asymmetric transfer hydrogenation reaction of ketones in water
Authors: Mao Jincheng , Guo Jun
Published: April 2009

The chiral amino amide 3 was derived from L‐proline and used for the [RuCl2(p‐cymene)]2‐catalyzed asymmetric transfer hydrogenation of prochiral ketones performed in water. Moderate to good chemical selectivities (up to 95% yield) and enantioselectivities (up to 90% ee) were obtained in the presence of 2 mol % of TBAB (n‐Bu4NBr) as the phase transfer catalyst. Chirality, 2010. © 2009 Wiley‐Liss, Inc.
Parallel kinetic resolution of D‐labelled 2‐aryl‐propionic and butanoic acids using quasi‐enantiomeric combinations of oxazolidin‐2‐ones
Authors: Coulbeck Elliot , Dingjan Marco , Eames Jason
Published: April 2009

The parallel kinetic resolution of racemic 2‐aryl‐2‐deuterio‐propionic and butanoic acids using an equimolar combination of quasi‐enantiomeric oxazolidin‐2‐ones is discussed. The levels of diastereoselectivity were high leading to enantiomerically pure D‐labeled products in good yield. Chirality, 2010. © 2009 Wiley‐Liss, Inc.
The asymmetric synthesis of (R,R)‐formoterol via transfer hydrogenation with polyethylene glycol bound Rh catalyst in PEG2000 and water
Authors: Huang Ling , Liu Juntao , Shan Wenjun , Liu Bao , Shi Anding , Li Xingshu
Published: April 2009

(R,R)‐formoterol was synthesized in seven steps with 4‐hydroxyl‐3‐nitro‐acetophenone as the starting material. The key intermediate, the chiral secondary alcohol 4, was prepared via Rh‐catalyzed asymmetric transfer hydrogenation with (S,S)‐PEGBsDPEN as the ligand and sodium formate as the hydrogen donor under mild conditions. With a mixture of PEG 2000 and water as the reaction media, the catalyst system could be recycled four times. Chirality, 2010. © 2009 Wiley‐Liss, Inc.
Lung cancer susceptibility and prognosis associated with polymorphisms in the nonhomologous end‐joining pathway genes
Authors: Tseng Ruo‐Chia , Hsieh Feng‐Jen , Shih Chuen‐Ming , Hsu Han‐Shui , Chen Chih‐Yi , Wang Yi‐Ching
Published: April 2009

BACKGROUND:

Nonsmall cell lung cancer (NSCLC) frequently exhibits genomic instability, such as high fractional allelic loss (FAL). Genomic instability may result from unrepaired or misrepaired double‐strand breaks (DSBs). The authors of this report postulated that polymorphisms in genes of the nonhomologous end‐joining (NHEJ) pathway, which is the major DSB repair pathway in mammalian cells, may modulate lung cancer susceptibility and prognosis.

METHODS:

Patients with NSCLC (n = 152) and a group of appropriate age‐matched and sex‐matched controls (n = 162) were subjected to genotype analysis of the NHEJ pathway genes x‐ray repair complementing defective repair in Chinese hamster cells 6 (Ku70) (reference single nucleotide polymorphism number [rs] 2267437), x‐ray repair complementing defective repair in Chinese hamster cells 5 (Ku80) (rs3835), x‐ray repair complementing defective repair in Chinese hamster cells 4 (XRCC4) (rs1805377), and DNA ligase IV (LIG4) (rs1805388). The gene‐gene interaction (joint effect), genotype‐environmental (ie, smoking) correlation, and genotype‐phenotype (ie, FAL) correlation were examined. The Kaplan‐Meier method and log‐rank tests were used to assess the prognostic effect.

RESULTS:

There was a significant association between the XRCC4 and LIG4 genotypes with NSCLC risk in an analysis of individual polymorphism associations, and the risk of NSCLC increased further in a combined analysis of multiple polymorphisms (adjusted odds ratio [OR], 8.74). The patients who had a homozygous variant guanine/guanine genotype of the XRCC4 gene had a poorer prognosis compared with other patients (P = .015). There was a significant difference between the patient smokers and controls for XRCC4 (adjusted OR, 2.67) and LIG4 (adjusted OR, 2.04). In addition, polymorphisms in XRCC4 and LIG4 were linked significantly with patients who had high FAL (adjusted OR, 2.03‐3.84).

CONCLUSIONS:

To the authors' knowledge, this is the first nested case‐control study to demonstrate a significant association between the polymorphisms of genes in the NHEJ pathway and lung cancer susceptibility and prognosis. The results may be useful for risk assessment and disease monitoring of patients with NSCLC. Cancer 2009. © 2009 American Cancer Society.
Anomalous Odd–Even Effects in Columnar and Smectic Phases of Discotic Tetraphenylenes
Authors: Hägele Constanze , Wuckert Eugen , Laschat Sabine , Giesselmann Frank
Published: April 2009

Rather uncommon but pronounced odd–even effects in the clearing temperatures of liquid crystals are found for three new homologous series of discotic tetraphenylenes (see figure). Detailed similarities to the well‐known odd‐even effects in calmitic mesogens point towards a more general understanding of odd‐even effects in liquid crystals.

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The phase transition temperatures in many homologous series of liquid crystals show odd‐even effects similar to the well‐known odd‐even effects in non‐mesogenic organic compounds like carboxylic acids. For discotic liquid crystals only a few series with a sufficient number of consecutive homologues are available and only a small part of these series show odd‐even effects at all. We now synthesized and investigated three series of discotic tetraphenylenes each ranging from the n=7 to the n=16 homologues. For these compounds an anomalous odd–even effect is found: The ascending and descending transition temperatures with increasing number of methylene groups in the side chains exhibit an inversion of this alternation which is always found between the n=12 and n=14 homologues. An overview of odd–even effects in liquid crystals is presented and we discuss the nature and the origin of odd–even effect in discotic mesogens.
From Iron Oxides to Infections
Authors: Newman Dianne K.
Published: April 2009

Cellular electron transfer under diverse anaerobic conditions is a primary topic of research conducted by the Newman group. In this Viewpoint, a summary is given of how a geobiological approach has been used to investigate these processes.

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The Transformative Innovations Needed by Green Chemistry for Sustainability
Authors: Anastas Paul T.
Published: April 2009

Green chemistry is discussed as a central design framework for the implementation of new scientific knowledge into everyday life. When adressed in such a manner, sustainability and economic viability are not necessarily mutually exclusive.

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Towards the Efficient, Total Glycan Utilization of Biomass
Authors: Mascal Mark , Nikitin Edward B.
Published: April 2009

From biomass to mass transportation: Waste biomass (newspaper, corn stover, straw, and wood) is converted into biofuel precursors and value‐added products in excellent yield using a simple, inexpensive process involving concurrent hydrolysis, dehydration, and substitution reactions in a biphasic reactor. The hemicellulose fraction of these substrates is simultaneously converted into furfural, and together these constitute an efficient means for the total exploitation of the carbohydrate content of biomass.

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Interplay of actors, scales, frameworks and regimes in the governance of biodiversity
Authors: Paavola Jouni , Gouldson Andrew , Kluvánková‐Oravská Tatiana
Published: April 2009

This article examines the key contributions of the political science and systems theory based literatures on environmental governance, and uses them to analyse the governance of biodiversity in Europe. The article suggests that the key insights of the two bodies of literature are a distinction between governance frameworks and regimes on one hand, and the importance of multifaceted and multiple scales on the other. These key insights draw attention to horizontal and vertical forms of interplay. The article suggests that interplay, both between actors and levels and between frameworks and regimes, is ubiquitous and ambivalent: it can either foster or hinder environmental governance. The article illustrates this discussion in the context of governance of biodiversity in Europe, highlighting how vertical and horizontal interplay between the governance framework for biodiversity and the broader institutional setting or regime have characterized the implementation of the Habitats Directive, both complicating and fostering the governance of biodiversity in Europe. Copyright © 2009 John Wiley & Sons, Ltd and ERP Environment.
Human natural Treg microRNA signature: Role of microRNA‐31 and microRNA‐21 in FOXP3 expression
Authors: Rouas Redouane , Fayyad‐Kazan Hussein , El Zein Nabil , Lewalle Philippe , Rothé Françoise , Simion Alexandru , Akl Haidar , Mourtada Mohamad , El Rifai Mohamad , Burny Arsène , Romero Pedro , Martiat Philippe , Badran Bassam
Published: April 2009

Treg are the main mediators of dominant tolerance. Their mechanisms of action and applications are subjects of considerable debate currently. However, a human microRNA (miR) Treg signature has not been described yet. We investigated human natural Treg and identified a signature composed of five miR (21, 31, 125a, 181c and 374). Among those, two were considerably under‐expressed (miR‐31 and miR‐125a). We identified a functional target sequence for miR‐31 in the 3′ untranslated region (3′ UTR) of FOXP3 mRNA. Using lentiviral transduction of fresh cord blood T cells, we demonstrated that miR‐31 and miR‐21 had an effect on FOXP3 expression levels. We showed that miR‐31 negatively regulates FOXP3 expression by binding directly to its potential target site in the 3′ UTR of FOXP3 mRNA. We next demonstrated that miR‐21 acted as a positive, though indirect, regulator of FOXP3 expression. Transduction of the remaining three miR had no direct effect on FOXP3 expression or on the phenotype and will remain the subject of future investigations. In conclusion, not only have we identified and validated a miR signature for human natural Treg, but also unveiled some of the mechanisms by which this signature was related to the control of FOXP3 expression in these cells.
Hydrotalcite‐Like Nanocrystals from Water‐in‐Oil Microemulsions
Authors: Bellezza Francesca , Cipiciani Antonio , Costantino Umberto , Nocchetti Morena , Posati Tamara
Published: April 2009

A water‐in‐oil microemulsion made up of a cetyltrimethylammonium bromide/n‐butanol/isooctane/MII and AlIII nitrate aqueous solution (MII = Mg or Ni or Zn) has been mixed with a microemulsion of the same composition but containing an ammonia solution instead of a metal nitrate solution. Collisions between the reverse micelles containing an MII and AlIII solution and those containing an NH3 solution form short‐lived dimers that act as reaction vessels and control the nucleation and growth of MgAl, NiAl or ZnAl hydrotalcite‐like compounds (HTlcs). The double water‐in‐oil microemulsion technique yields colloidal dispersions of nanoparticles whose size and shape were examined by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The colloidal particles were between 50 and 100 nm depending on the composition of the microemulsions (water‐to‐surfactant and oil‐to‐water molar ratios). The separation of the nanoparticles from the reaction medium produces a gel made up of surfactant‐free particles. HTlc nanocrystals were recovered from the gel (reaction medium), washed, and dried. They were then studied by chemical and thermogravimetric analyses, X‐ray powder diffraction, N2‐adsorption and BET surface analysis and scanning electron microscopy (SEM). The AlIII/(MII + AlIII) molar ratio of the recovered HTlc nanocrystals was between 0.24 and 0.29, and the basal spacing was about 8 Å, a value in agreement with the presence of charge compensating bromide anions in the interlayer region. The proposed technique allows for HTlc nanocrystals to be obtained with a relatively high surface area with values ranging between 50 and 110 m2/g. The SEM analyses show that the nanoparticles are aggregated to give rise to complex spherical or rod‐shaped microstructures.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
The Contribution of Electrospray Mass Spectrometry to the Study of Metal Complexes: The Case of Copper(II)–Dipeptide Systems
Authors: Maccarrone Giuseppe , Caruso Rosario , Contino Annalinda , Giuffrida Alessandro , Messina Marianna , Cucinotta Vincenzo
Published: April 2009

Following a previous thermodynamic and spectroscopic investigation, 13 copper(II)–dipeptide complexes have been characterized by electrospray ionization mass spectrometry (ESI‐MS) and visible optical spectroscopy. The data obtained confirm the presence of the species singled out by the thermodynamic approach, showing the ability of electrospray mass spectrometry to give evidence of the presence of a water molecule in the copper(II) in‐plane coordination. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Synthesis, Structure and Catalysis of Tetranuclear Copper(II) Open Cubane for Henry Reaction on Water
Authors: Jammi Suribabu , Punniyamurthy Tharmalingam
Published: April 2009

The copper(II) open cubane 1 has been synthesized and its structure determined. It is insoluble in water and efficiently catalyzes the Henry reaction with high yield. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Ratiometric Fluorescence Sensing of Fluoride Ions by an Asymmetric Bidentate Receptor Containing a Boronic Acid and Imidazolium Group
Authors: Xu Zhaochao , Kim Sook Kyung , Han Su Jung , Lee Chongmok , Kociok‐Kohn Gabriele , James Tony D. , Yoon Juyoung
Published: April 2009

The synthesis of the first examples of anion receptors that utilize boron–fluoride interactions and (C–H)+···F–‐type ionic hydrogen‐bond interactions in the binding of F ions is reported herein. o‐, m‐, and p‐Phenylboronic acids were linked to naphthoimidazolium through a methylene group. On the basis of fluorescence and 19F NMR studies, we have confirmed that the addition of fluoride to a boron center occurs prior to the formation of (C–H)+···F–‐type ionic hydrogen bond with the imidazolium moiety. More importantly, these investigations have demonstrated that only the receptor bearing the ortho‐directed boron and imidazolium exhibits enhanced fluoride binding. The increased binding ability of the asymmetric bidentate receptor of ortho‐boronic acid and imidazolium towards F– enables it to sense fluoride ions in a 95:5 CH3CN/HEPES aqueous solution. The fluorescence responses to different anions were also explored; the ortho‐boron‐imidazolium receptor displayed ratiometric fluorescence changes and a high selectivity towards fluoride ions over other anions (Cl–, Br–, CH3CO2–, HSO4–, and H2PO4–).(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Palladium‐Catalysed Multicomponent Aminocarbonylation of Aryl or Heteroaryl Halides with [Mo(CO)6] and Aryl‐ or ­Heteroarylamines Using Conventional Heating
Authors: Begouin Agathe , Queiroz Maria‐João R. P.
Published: April 2009

Di(hetero)arylamides have been synthesized in short reaction times by palladium‐catalysed multicomponent aminocarbonylation of either electron‐deficient or electron‐rich heteroaryl halides and p‐iodoanisole with several arylamines bearing either electron‐donating or ‐withdrawing groups and aminopyridines using [Mo(CO)6] as a solid CO source and conventional heating. Starting from heteroaryl bromides, a palladacycle with tBu3PHBF4 as ligand is required together with DBU as a base in dioxane and a temperature of 125 °C. From (hetero)aryl iodides, Pd(OAc)2 without a ligand and DBU were used in dioxane at 110 °C. Under the latter conditions we were able to apply this reaction to deactivated aminopyridines to obtain the corresponding di(hetero)arylamides. We have demonstrated that these reactions can be performed under conventional heating (110–125 °C) to yield the corresponding di(hetero)arylamides in moderate‐to‐high yields in short reaction times (from 1–3 h) with no need for MW irradiation. A N‐substituted isoindoline‐1,3‐dione from 2‐iodobenzoic acid or methyl 2‐iodobenzoate and p‐anisidine through a one‐step carbonylative cyclization reaction was also obtained. Thus, we have extended the scope of thispalladium‐catalysed aminocarbonylation reaction with [Mo(CO)6] to several (hetero)aryl substrates using conventional heating. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Molecular Designs and Syntheses of Organic Dyes for Dye‐Sensitized Solar Cells
Authors: Ooyama Yousuke , Harima Yutaka
Published: April 2009

Dye‐sensitized solar cells (DSSCs) based on organic dyes adsorbed on nanocrystalline TiO2 electrodes have received considerable attention because of their high incident solar light‐to‐electricity conversion efficiency and low cost of production. A number of organic dyes have so far been developed, and the relationship between their chemical structures and the photovoltaic performances of DSSCs based on the dyes has been examined. To create high‐performance DSSCs, it is important to develop effective organic dye sensitizers, which should be optimized for the chemical structures to possess good light‐harvesting features, to provide good electron communication between the dyes and a TiO2 electrode, and to control the molecular arrangements on the TiO2 electrode. The aim of this microreview is to highlight the design and synthesis of organic dyes for DSSCs based on recent work of organic chemists. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Adoptive Relationships in West Africa
Authors: Unterstell Rembert
Published: April 2009

Social anthropologist Erdmute Alber investigates changes in family networks on the “Dark Continent” – and has an eye on Europe as well
The Janus‐faced Composer
Authors: Konrad Ulrich
Published: April 2009

The work of Winfried Zillig and other notable German musicians after 1933 was characterised by contradictions that are hard to fathom: Artistically ambitious modernism coexisted side by side with the mindless currying of favour to ideological propaganda
Reproduction – A Delicate Balance
Authors: Henke Alexander , Michel Caroline , Gromoll Jörg
Published: April 2009

No lutropin, no offspring: hormones play a decisive role in reproduction. Their molecular mechanisms are now being deciphered
Expansion and Excellence
Authors: Streier Eva‐Maria
Published: April 2009

India, as a research country, faces great challenges
Exercise preferences among patients with head and neck cancer: Prevalence and associations with quality of life, symptom severity, depression, and rural residence
Authors: Rogers Laura Q. , Malone James , Rao Krishna , Courneya Kerry S. , Fogleman Amanda , Tippey Amaris , Markwell Stephen J. , Robbins K. Thomas
Published: April 2009

Background

Our aim was to determine exercise preferences among patients with head and neck cancer and their associations with quality of life, symptom severity, depression, and rural residence.

Methods

This study involved a cross‐sectional chart review and self‐administered survey, with 90 outpatients with head and neck cancer (response rate = 83%).

Results

The majority were <65 years old (65%), male (78%), and white (96%) with stage ≥III (81%). Lack of preference was the most frequent option for counseling source (66%), counseling delivery (47%), and exercise variability (52%). Popular specific preferences included outdoors (49%), morning (47%), and alone (50%). Significant adjusted associations occurred for patients' interest with lower functional well‐being, alone with higher functional well‐being, and morning with higher total quality of life and emotional, social, and functional well‐being. No significant associations occurred with symptoms, depression, or rural residence.

Conclusion

Patients with head and neck cancer may be open to a variety of exercise options. Quality of life may influence interest and preference for exercising alone or in the morning. © 2009 Wiley Periodicals, Inc. Head Neck, 2009
Detection of survivin and p53 in human oral cancer: Correlation with clinicopathologic findings
Authors: Khan Zakir , Tiwari Ram P. , Mulherkar Rita , Sah Nand K. , Prasad Godavarthi BKS , Shrivastava Braj R. , Bisen Prakash S.
Published: April 2009

Background

Survivin, an inhibitor of apoptosis, is overexpressed in cancer. It has been implicated in both prevention of apoptosis and cell cycle regulation. We investigated the distribution of antiapoptotic protein survivin in 29 oral squamous cell carcinoma (OSCC) and 16 oral premalignant lesions. It has been suggested that wild‐type p53 represses survivin expression. Therefore, we investigated the status of p53 in relation to survivin to determine the potential involvement in oral tumorigenesis.

Methods

Oral cancer tissues were freshly obtained at the time of surgery and classified as per general rules of head and neck cancer (TNM classification). Immunohistochemistry and reverse transcriptase‐polymerase chain reaction were conducted to study the expression of survivin and p53. The Fisher's exact test was employed to determine the association of survivin and p53 with clinicopathologic parameters of the subjects being studied.

Results

Positive staining for survivin was found in 72% OSCC and 44% oral premalignant lesions with no immunoreactions in the corresponding normal tissues. For p53, 59% OSCC, 38% premalignant lesions, and 14% normal tissues were positive. Importantly, about half of the p53‐positive OSCC and premalignant tissues also showed survivin positivity (28% OSCC and 18% premalignant lesions). Further, it is observed that the number of survivin positive cells was significantly higher in the p53‐positive group. Survivin is expressed in a varying proportion of cells, and in majority of patients it was localized in cytoplasm, whereas p53 is strictly restricted to the nucleus. The survivin expression levels in both primary OSCC and premalignant lesions were significantly higher than in normal oral tissues (OSCC, p < .0008; premalignant lesions, p < .04). No significant correlations between survivin and p53 expression with clinicopathologic parameters were found.

Conclusions

Frequent overexpression of apoptosis regulators, survivin and p53, in OSCC as well as in oral premalignant lesions were found. Overexpression of these 2 markers in premalignant lesions suggest a role in early stages of oral carcinogenesis. © 2009 Wiley Periodicals, Inc. Head Neck, 2009
Local recurrences and second primary tumors from squamous cell carcinoma of the oral cavity: A retrospective analytic study of 500 patients
Authors: González‐García Raúl , Naval‐Gías Luis , Román‐Romero Leticia , Sastre‐Pérez Jesús , Rodríguez‐Campo Francisco J.
Published: April 2009

Background.

The purpose of this study was to evaluate the incidence of local recurrences (LRs) and second primary tumors (SPTs) from squamous cell carcinoma (SCC) of the oral cavity primarily treated with surgery and to further study their relationship with several primary tumor clinical and pathological features.

Methods.

Five hundred of 522 patients with SCC of the oral cavity primarily treated with surgery were retrospectively analyzed for the appearance of LRs and SPTs within the oral cavity. All patients with SPTs fulfilled the Warren & Gates criteria. Several clinical features were analyzed. Histological study included TNM classification, tumor size, tumor thickness, surgical margins, perineural infiltration, peritumoral inflammation, and bone involvement. In the univariant analysis, the possible association between different clinical and pathological features and the presence of LRs or SPTs was analyzed by means of the chi‐square test for categorical data and the Student's t test for parametric data. The appearance of LRs and SPTs was also studied by binary logistic regression as time‐dependant phenomena, in the univariant analysis. Logistic regression was also used for the multivariant analysis between the selected variables. The Kaplan‐Meier method was used to estimate the probability of SPT‐ or LR‐free survival.

Results.

The mean duration of the follow‐up period was 52.27 ± 49.52 months. At the end of this time, 53.82% of the patients were alive without evidence of disease, whereas 31.48% had specifically died of disease. Twenty‐eight (5.6%) patients developed an SPT within the oral cavity, whereas 95 (19%) patients developed an LR during the whole follow‐up period. The 5‐year disease‐specific survival rate for the whole series was 67.2%, in contrast to 34.9% in the group of patients with SPT and/or LR. In relation to the univariant analysis, T classification, TNM staging, pT classification, surgical margins, bone involvement, and postoperative radiotherapy (RT) were found to be predictive for LR. In relation to the multivariant analysis, only postoperative RT and bone involvement were predictive for the development of LR.

Conclusion.

The identification of preoperative and postoperative clinical and pathological features that prelude a higher risk for the appearance of LRs and/or SPTs may be of potential interest in determining which patients should benefit of a closer regular follow‐up. When considering together the whole clinical and pathological features, only postoperative RT and bone involvement were predictive for the development of LRs. Because of the poor survival rate of the affected patients, we strongly recommend aggressive surgical treatment following the appearance of an SPT or LR. © 2009 Wiley Periodicals, Inc. Head Neck, 2009
Analysis of free flap viability based on recipient vein selection
Authors: Francis David O. , Stern Ryan E. , Zeitler Daniel , Izzard Mark , Futran Neal D.
Published: April 2009

Background.

Venous anastomotic failure is the primary reason for microvascular free tissue transfer failure. Donor and recipient veins can be oriented in the same longitudinal axis (end‐to‐end anastomosis), or the donor vein can be anastomosed to the internal jugular vein in an end‐to‐side configuration. No consensus on the optimal anastomosis configuration exists. We sought to evaluate whether type of venous anastomosis impacts flap survival rate.

Methods.

Data were collected on all patients undergoing microvascular free flap reconstruction of head and neck defects at the University of Washington between August 1993 and April 2007. Flaps with a single venous anastomosis were analyzed. Flaps were stratified into those with end‐to‐end and end‐to‐side anastomoses. Survival rates were compared between groups using bivariate and multivariate techniques.

Results.

Inclusion criteria were met by 786 free flaps; 87% performed in an end‐to‐end and 13% in an end‐to‐side configuration. Flap re‐exploration and failure rate were 4.3% and 1.1%, respectively. In multivariate analysis, there was no difference in odds of flap re‐exploration (OR .70, 95% CI .23–2.18) or flap failure whether or not an end‐to‐end or end‐to‐side anastomosis was performed (OR 2.09, 95% CI .38–11.5).

Conclusions.

In this large cohort of patients, we found no difference in the odds of flap re‐exploration or failure based on venous anastomotic configuration. Reconstructive surgeons should have both anastomotic techniques in their repertoire to optimize the success of every flap. © 2009 Wiley Periodicals, Inc. Head Neck, 2009
Predictors of outcome for advanced‐stage supraglottic laryngeal cancer
Authors: Ganly Ian , Patel Snehal G. , Matsuo Jeanette , Singh Bhuvanesh , Kraus Dennis H. , Boyle Jay , Wong Richard J. , Lee Nancy , Pfister David G. , Shaha Ashok R. , Shah Jatin P.
Published: April 2009

Background.

The objective of this study was to report our experience in the management of patients with advanced‐stage supraglottic laryngeal carcinoma and to identify factors predictive of outcome.

Methods.

In total, 181 patients with advanced‐stage supraglottic laryngeal carcinoma were treated at Memorial Sloan‐Kettering Cancer Center between 1984 and 1998. Sixty‐nine (38%) patients were treated by surgery ± postoperative radiotherapy (SRT), 93 (52%) by chemoradiotherapy (CTRT), and 19 (10%) by radiotherapy alone (RT). Survival outcomes were calculated using the Kaplan‐Meier method. Predictors of outcome were identified using multivariate analysis.

Results.

The‐5 year overall survival (OS) and disease‐specific survival (DSS) were 53% and 71%, respectively. Patients treated with SRT and CTRT had comparable outcomes. The main independent predictors of OS and DSS were age greater than 60 years and stage of the neck at presentation.

Conclusion.

Regardless of index treatment, age over 60 years and clinical stage of the neck at presentation were the main independent predictors of OS and DSS. © 2009 Wiley Periodicals, Inc. Head Neck, 2009
Theoretical study of the prion protein based on the fragment molecular orbital method
Authors: Ishikawa Takeshi , Ishikura Takakazu , Kuwata Kazuo
Published: April 2009

We performed fragment molecular orbital (FMO) calculations to examine the molecular interactions between the prion protein (PrP) and GN8, which is a potential curative agent for prion diseases. This study has the following novel aspects: we introduced the counterpoise method into the FMO scheme to eliminate the basis set superposition error and examined the influence of geometrical fluctuation on the interaction energies, thereby enabling rigorous analysis of the molecular interaction between PrP and GN8. This analysis could provide information on key amino acid residues of PrP as well as key units of GN8 involved in the molecular interaction between the two molecules. The present FMO calculations were performed using an original program developed in our laboratory, called “Parallelized ab initio calculation system based on FMO (PAICS)”. © 2009 Wiley Periodicals, Inc. J Comput Chem 2009
Tuning aromaticity in trigonal alkaline earth metal clusters and their alkali metal salts
Authors: JimÉnez‐halla J. Oscar C. , Matito Eduard , Blancafort LluÍs , Robles Juvencio , Solà Miquel
Published: April 2009

In this work, we analyze the geometry and electronic structure of the [XnM3]n−2 species (M = Be, Mg, and Ca; X = Li, Na, and K; n = 0, 1, and 2), with special emphasis on the electron delocalization properties and aromaticity of the cyclo‐[M3]2− unit. The cyclo‐[M3]2− ring is held together through a three‐center two‐electron bond of σ‐character. Interestingly, the interaction of these small clusters with alkali metals stabilizes the cyclo‐[M3]2− ring and leads to a change from σ‐aromaticity in the bound state of the cyclo‐[M3]2− to π‐aromaticity in the XM3− and X2M3 metallic clusters. Our results also show that the aromaticity of the cyclo‐[M3]2− unit in the X2M3 metallic clusters depends on the nature of X and M. Moreover, we explored the possibility for tuning the aromaticity by simply moving X perpendicularly to the center of the M3 ring. The Na2Mg3, Li2Mg3, and X2Ca3 clusters undergo drastic aromaticity alterations when changing the distance from X to the center of the M3 ring, whereas X2Be3 and K2Mg3 keep its aromaticity relatively constant along this process. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009
Comparison of photobioreactors and optimal light regime for rapid vegetative propagation of transgenic Undaria pinnatifida gametophytes
Authors: Deng Xiangyuan , Qin Song , Zhang Yichen , Jiang Peng
Published: April 2009

BACKGROUND: Previously, tachyplesin gene (tac) has been successfully transferred into Undaria pinnatifida gametophytes using the method of microprojectile bombardment transformation. The objectives of this study were to compare and evaluate the performance of bubble‐column and airlift bioreactors to determine a preferred configuration of bioreactor for vegetative propagation of transgenic U. pinnatifida gametophytes, and to then investigate the influence of light on vegetative propagation of these gametophytes, including incident light intensity, photoperiod and light quality to resolve the problems of rapid vegetative propagation within the selected bioreactor.

RESULTS: Experimental results showed that final dry cell density in the airlift bioreactor was 12.7% higher than that in the bubble‐column bioreactor under the optimal aeration rate of 1.2 L air min−1 L−1 culture. And a maximum final dry cell density of 2830 mg L−1 was obtained within the airlift bioreactor using blue light at 40 µmol m−2 s−1 with a light/dark cycle of 14/10 (h). Polymerase chain reaction (PCR) analysis indicated that genes (bar and tac) were not lost during rapid vegetative propagation within the airlift bioreactor.

CONCLUSION: The airlift bioreactor was shown to be much more suitable for rapid vegetative propagation of transgenic U. pinnatifida gametophytes than the bubble‐column bioreactor in the laboratory. The use of blue light allows improvement of vegetative propagation of transgenic U. pinnatifida gametophytes. Copyright © 2009 Society of Chemical Industry
A new method for the determination of the relative affinity of a ligand against various DNA sequences by electrospray ionization mass spectrometry. Application to a polyamide minor groove binder
Authors: Buchmann William , Boutorine Alexandre , Halby Ludovic , Tortajada Jeanine , De Pauw Edwin
Published: April 2009

A new method for the determination of the relative affinity of a ligand against various dsDNA sequences is presented by using electrospray ionization time‐of‐flight mass spectrometry (ESI‐QTOF) mass spectrometry. The principle is described here through the complexation of double‐stranded DNA by a polyamide ligand including twelve N‐methylpyrrole rings. However this method could be applied to other ligands especially when dissociation constants (Kd) are in nanomolar range. This method does not require knowing the ligand concentration accurately. It allows determination of the relative affinity of a ligand against various dsDNA sequences for 1 : 1 complex stoichiometries in a quick manner without labeling. Copyright © 2009 John Wiley & Sons, Ltd.
Phenotype and chondrogenic differentiation of mesenchymal cells from adipose tissue of different species
Authors: Martínez‐Lorenzo María José , Royo‐Cañas María , Alegre‐Aguarón Elena , Desportes Paula , Castiella Tomás , García‐Álvarez Felícito , Larrad Luis
Published: April 2009

Mesenchymal stem cells (MSCs) are multipotent cells capable of differentiating into several mesoderm lineages. They have been isolated from different tissues, such as bone marrow, adult peripheral blood, umbilical cord blood, and adipose tissue. The aim of this study was to analyze the differences in proliferation and phenotype of adipose tissue‐derived MSCs from three different species, and to evaluate their capacity to differentiate into chondrocytes in vitro. A comparative study of cultured human, rabbit, and sheep mesenchymal cells from adipose tissue was carried out, and the main morphological parameters, proliferative activity, and expression of surface markers were characterized. Proliferation and flow cytometry data showed species‐related differences between animal and human MSCs. Histological staining suggested that rabbit and sheep mesenchymal cells were able to differentiate into chondrocytic lineages. Human mesenchymal cells, though they could also differentiate, accomplished it with more difficulty than animal MSCs. These results could help to explain the differences in the chondrogenic capacity of sheep and rabbit MSCs when they are used as animal models compared to human mesenchymal cells in a clinical assay. © 2009 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 27:1499–1507, 2009