bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical sensing materials. I. Electrically conductive SEBS copolymer systems
Authors: Pavlovsky S. , Siegmann A.
Published: May 2009

Chemical sensing materials based on conductive carbon black (CB) filled [styrene‐ethylene butylene‐styrene] triblock‐copolymers (SEBS) were investigated. Several types of SEBS copolymers were studied, differing in composition and melt viscosity. The sensing is based on electrical conductivity changes upon solvent sorption/desorption. Compression molding SEBS composites containing various amounts of CB were prepared. Their electrical conductivity was measured and samples containing CB, preferentially located in the continuous ethylene/butylene (EB) phase, at a level near the corresponding percolation threshold were used for the sensing experiments. The conductivity was measured during several exposure/drying cycles. Structure characterization included scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), and calorimetry (DSC). The SEBS composites exhibit large reversible changes in conductivity upon exposure to a limited number of solvents, e.g., acetone, n‐heptane, and air drying cycles. This behavior was related to the sorption kinetics, affected by the solvent characteristics (solubility parameter, polarity, molecular volume and vapor pressure). The samples' resistance tended to return to their initial value upon short drying of acetone, and longer drying of other studied solvents. The nature of the SEBS, the CB content, and mixing temperature are all significant parameters, determining the sample's structure and the resultant sensing property. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009
Model selection for generalized linear models with factor‐augmented predictors
Authors: Ando Tomohiro , Tsay Ruey S.
Published: May 2009

This paper considers generalized linear models in a data‐rich environment in which a large number of potentially useful explanatory variables are available. In particular, it deals with the case that the sample size and the number of explanatory variables are of similar sizes. We adopt the idea that the relevant information of explanatory variables concerning the dependent variable can be represented by a small number of common factors and investigate the issue of selecting the number of common factors while taking into account the effect of estimated regressors. We develop an information criterion under model mis‐specification for both the distributional and structural assumptions and show that the proposed criterion is a natural extension of the Akaike information criterion (AIC). Simulations and empirical data analysis demonstrate that the proposed new criterion outperforms the AIC and Bayesian information criterion. Copyright © 2009 John Wiley & Sons, Ltd.
Time‐resolved spectral measurements of delayed luminescence from a single soybean seed: effects of thermal damage and correlation with germination performance
Authors: Lanzanò Luca , Sui Li , Costanzo Evelina , Gulino Marisa , Scordino Agata , Tudisco Salvatore , Musumeci Francesco
Published: May 2009

Delayed luminescence from a single dry soybean seed was investigated in both spectral and time domains, under different excitation wavelengths. Emission spectra were collected, under 337 nm laser excitation, from native and artificially deteriorated seeds and the time‐dependence of different spectral components was analyzed in detail. The single seed viability was evaluated through observation of germination properties after imbibition and compared with different parameters related to the luminescence kinetics. The significant correlation found between single seed delayed luminescence parameters and germination capability strongly validates the connection of this phenomenon with the functional state of the system and suggests the development of a non‐invasive technique for seed quality determination. Copyright © 2009 John Wiley & Sons, Ltd.
The fluorescence enhancement of quercetin–nucleic acid system and the analytical application
Authors: Liu Yuan , Wu Xia , Zhou Haiping , Liu Xiaoyu , Zhang Fengju , Yang Jinghe
Published: May 2009

Nucleic acid can greatly enhance the fluorescence intensity of quercetin in HMTA‐HCl (pH 5.5) buffer. The enhanced intensity is in proportion to the concentration of nucleic acids in the range 5.0 × 10−9 to 1.0 × 10−6 g/mL for fsDNA, 5.0 × 10−9 to 7.0 × 10−7 g/mL for ctDNA and 5.0 × 10−9 to 1.0 × 10−6 g/mL for yRNA, and their detection limits (S/N = 3) are 3.5 × 10−9, 7.8 × 10−10 and 2.6 × 10−9 g/mL, respectively. In comparison with most reported fluorescent probes for the determination of nucleic acids, the proposed probe has higher sensitivity and lower toxicity. The interaction investigation indicates that quercetin binds with double‐strand DNA in groove binding mode, resulting in fluorescence enhancement of this system. Copyright © 2009 John Wiley & Sons, Ltd.
Interaction between felodipine and bovine serum albumin: fluorescence quenching study
Authors: Mote U. S. , Bhattar S. L. , Patil S. R. , Kolekar G. B.
Published: May 2009

The fluorescence quenching spectrum of bovine serum albumin (BSA) was investigated in the presence of felodipine (FLD) by spectroscopic methods including fluorescence spectroscopy and UV–Vis absorption spectroscopy. Stern–Volmer quenching was successfully applied and the corresponding thermodynamic parameters, namely enthalpy change (ΔH), free energy change (ΔG) and entropy change (ΔS) at different temperatures (304, 314 and 324 K) were calculated according to the Van't Hoff relation. This revealed that the hydrophobic interaction plays a major role in stabilizing the complex. The fluorescence spectrum of BSA was studied in presence of various concentrations of SDS surfactant. The distance (r) between donor (BSA) and acceptor (FLD) was obtained according to fluorescence resonance energy transfer (FRET). The synchronous fluorescence spectroscopy was used to investigate the effect of FLD on BSA molecule. The result shows that the conformation of BSA was changed in the presence of felodipine. Copyright © 2009 John Wiley & Sons, Ltd.
Conformation dependence of the CαDα stretch mode in peptides. II. Explicitly hydrated alanine peptide structures
Authors: Mirkin Noemi G. , Krimm Samuel
Published: May 2009

Our previous studies of the potential utility of the CαDα stretch frequency, ν(CD), as a tool for determining conformation in peptide systems (Mirkin and Krimm, J Phys Chem A 2004, 108, 10923–10924; 2007, 111, 5300–5303) dealt with the spectroscopic characteristics of isolated alanine peptides with αR, β, and polyproline II structures. We have now extended these ab initio calculations to include various explicit‐water environments interacting with such conformers. We find that the structure‐discriminating feature of this technique is in fact enhanced as a result of the conformation‐specific interactions of the bonding waters, in part due to our finding (Mirkin and Krimm, J Phys Chem B 2008, 112, 15268) that CαDα…O(water) hydrogen bonds can be present in addition to those expected between water and the CO and NH of the peptide groups. In fact, ν(CD) is hardly affected by the latter bonding but can be shifted by up to 70 cm−1 by the former hydrogen bonds. We also discuss the factors that will have to be considered in developing the molecular dynamics (MD) treatment needed to satisfactorily take account of the influence of outer water layers on the structure of the first‐layer water molecules that hydrogen bond to the peptide backbone. © 2009 Wiley Periodicals, Inc. Biopolymers 91: 791–800, 2009.

This article was originally published online as an accepted preprint. The “Published Online” date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com
Adolescent well‐being and supporting contexts: A comparison of adolescents in Ireland and Florida
Authors: McGrath Brian , Brennan M. A. , Dolan Pat , Barnett Rosemary
Published: May 2009

The purpose of this research was to examine the extent to which social support and wider community perceptions/engagements among adolescents are connected with well‐being. We compared adolescents in two different societal contexts, Florida in the United States and County Offaly, in Ireland, and posed the questions: What are the key predictors of subjective well‐being from the various sources of support, and to what extent does the impact of social support on well‐being vary across these two societies? Questionnaires were completed and returned for 607 respondents (322 in the Irish study and 285 in the Florida study). A variety of scales were adopted and designed to operationalize our key concepts of: Adolescent well‐being, social support, school satisfaction, neighbourhood quality of life and community/voluntary participation. Our results indicate that informal social support and school satisfaction were the strongest predictors of youth well‐being in both locations, despite some differences in terms of individual influencing variables. From informal sources, emotional support from friends and advice/concrete/esteem support from parents emerged as important predictive dimensions. Liking school, perceptions of doing well in school were the main predictors of school satisfaction in Ireland while, in Florida, student camaraderie and the experience of bullying emerged as significant. Copyright © 2009 John Wiley & Sons, Ltd.
First report on the use of a novel self‐expandable stent for treatment of ST elevation myocardial infarction
Authors: IJsselmuiden Alexander , Verheye Stefan
Published: May 2009

A 69‐year‐old female underwent primary percutaneous coronary intervention with a Stentys™ self‐expandable stent. Potential benefits of this stent are less intimal proliferation, reduced need for predilatation, reduced risk of malapposition and distal embolization. After written informed consent, the occluded proximal left anterior descending artery was successfully treated with thrombosuction, followed by implantation of the self‐expandable stent. Intravascular ultrasound examination postprocedure and at 5 days showed good stent apposition and it appeared that the vessel diameter had increased probably due to self‐expanding properties of the stent and relief of coronary spasm. The patient was discharged event‐free. A larger patient cohort is needed to investigate safety and feasibility of this novel stent. © 2009 Wiley‐Liss, Inc.
Thrombus extrusion through filter wire basket
Authors: Cooper Robert M. , Morris John L.
Published: May 2009

A 56‐year old male presenting with Acute Coronary Syndrome was found to have a large thrombus partially including a bypass graft bare metal stent. This thrombus was removed using a filter wire. The thrombus burden was so large that it caused extension through the filter wire basket, narrowly avoiding distal embolisation. © 2009 Wiley‐Liss, Inc.
Transradial renal stenting: Why and how
Authors: Trani Carlo , Tommasino Antonella , Burzotta Francesco
Published: May 2009

Transradial vascular access for invasive procedures is gaining increasingly acceptance due to reduced access‐site complications and improved patient's comfort compared with transfemoral. However, the adoption of transradial access in peripheral vascular procedures is actually limited by anatomical and technical considerations. Yet, among all the peripheral vascular districts, the renal one seems to be particularly suitable for transradial approach. In this article, we discuss the rationale for preferring the radial approach instead of femoral and review the specific technical issues related to transradial renal artery stenting (RAS). © 2009 Wiley‐Liss, Inc.
Transcatheter aortic valve closure to treat severe aortic regurgitation in a patient failing stage I palliation for hypoplastic left heart syndrome
Authors: Riede Frank‐Thomas , Kostelka M. , Dähnert I.
Published: May 2009

We present a patient with borderline left ventricle, in whom significant aortic regurgitation after failed attempt of biventricular repair with balloon valvuloplasty and consecutive Norwood stage 1 procedure substantially contributed to persisting hemodynamic instability. Transcatheter closure of the aortic valve using an Amplatzer® septal occluder was performed and led to clinical stabilization. At medium‐term follow‐up, there was neither residual aortic regurgitation nor obstruction of the coronary artery origins.© 2009 Wiley‐Liss, Inc.
EXAFS Study of Dopant Ions with Different Charges in Nanocrystalline Anatase: Evidence for Space–Charge Segregation of Acceptor Ions
Authors: Knauth Philippe , Chadwick Alan V. , Lippens Pierre E. , Auer Gerhard
Published: May 2009

Nanocrystalline TiO2 (anatase) is an essential oxide for environment and energy applications. A combination of EXAFS spectroscopy and DFT calculations on a series of dopants with quite similar ion radius, but increasing ion charge, show boundary space charge segregation of acceptor cations. The picture illustrates the Fourier‐transformed EXAFS spectrum for Sn4+‐doped TiO2.

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A series of dopants, including acceptor ions (Zn2+, Y3+), isovalent ions (Zr4+, Sn4+) as well as a donor ion (Nb5+), were studied by EXAFS spectroscopy in nanocrystalline TiO2 anatase powders and nanoceramics. Similar results were found for nanocrystalline powders and nanocrystalline ceramics, made by hot‐pressing the powders. Boundary segregation was observed for the acceptor ions yttrium and zinc, whereas tin, zirconium and niobium ions were placed on substitutional bulk sites and did not segregate, whatever their concentration. These results can be interpreted based on defect thermodynamics, in the framework of a space charge segregation model with positive boundary core, due to excess oxide ion vacancies, and negative space charge regions, where ionized acceptors are segregated.
Our Current Understanding of the Impact of Aerosols on Climate Change
Authors: Prather Kimberly A.
Published: May 2009

Aerosols constitute a climate and health risk via both direct and indirect effects. In this Viewpoint, recent developments in aerosol research and available instrumentation are discussed in the context of environmental change.

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Coming of Age: Sustainable Iron‐Catalyzed Cross‐Coupling Reactions
Authors: Czaplik Waldemar Maximilian , Mayer Matthias , Cvengroš Ján , von Wangelin Axel Jacobi
Published: May 2009

Iron‐catalyzed cross‐coupling reactions have, over the past years, developed to maturity and today are an integral part of the organic chemist's toolkit. They benefit from low costs, operational simplicity, and high reactivity and thus constitute the “green” sister of the palladium and nickel establishment. This timely Review traces back major achievements, discusses their mechanistic background, and highlights numerous applications to molecular synthesis.

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Iron‐catalyzed carbon–carbon bond‐forming reactions have matured to an indispensable class of reactions in organic synthesis. The advent of economically and ecologically attractive iron catalysts in the past years has stepped up the competition with the established palladium and nickel catalyst systems that have dominated the field for more than 30 years, but suffer from high costs, toxicity, and sometimes low reactivity. Iron‐catalyzed protocols do not merely benefit from economic advantages but entertain a rich manifold of reactivity patterns and tolerate various functional groups. The past years have witnessed a rapid development with ever‐more‐efficient protocols for the cross‐coupling between alkyl, alkenyl, alkynyl, aryl, and acyl moieties becoming available to organic chemists. This Review intends to shed light onto the versatility that iron‐catalyzed cross‐coupling reactions offer, summarize major achievements, and clear the way for further use of such superior methodologies in the synthesis of fine chemicals, bioactive molecules, and materials.
Changes in gene expression and morphology of mouse embryonic stem cells on differentiation into insulin‐producing cells in vitro and in vivo
Authors: Naujok Ortwin , Francini Flavio , Picton Sally , Bailey Clifford J. , Lenzen Sigurd , Jörns Anne
Published: May 2009

Background

Embryonic stem (ES) cells have the potential to produce unlimited numbers of surrogate insulin‐producing cells for cell replacement therapy of type 1 diabetes mellitus. The impact of the in vivo environment on mouse ES cell differentiation towards insulin‐producing cells was analysed morphologically after implantation.

Methods

ES cells differentiated in vitro into insulin‐producing cells according to the Lumelsky protocol or a new four‐stage differentiation protocol were analysed morphologically before and after implantation for gene expression by in situ reverse transcription polymerase chain reaction and protein expression by immunohistochemistry and ultrastructural analysis.

Results

In comparison with nestin positive ES cells developed according to the reference protocol, the number of ES cells differentiated with the four‐stage protocol increased under in vivo conditions upon morphological analysis. The cells exhibited, in comparison to the in vitro situation, increased gene and protein expression of Pdx1, insulin, islet amyloid polypeptide (IAPP), the GLUT2 glucose transporter and glucokinase, which are functional markers for glucose‐induced insulin secretion of pancreatic beta cells. Renal sub‐capsular implantation of ES cells with a higher degree of differentiation achieved by in vitro differentiation with a four‐stage protocol enabled further significant maturation for the beta‐cell‐specific markers, insulin and the co‐stored IAPP as well as the glucose recognition structures. In contrast, further in vivo differentiation was not achieved with cells differentiated in vitro by the reference protocol.

Conclusions

A sufficient degree of in vitro differentiation is an essential prerequisite for further substantial maturation in a beta‐cell‐specific way in vivo, supported by cell‐cell contacts and vascularisation. Copyright © 2009 John Wiley & Sons, Ltd.
Screening for binge eating disorders using the Patient Health Questionnaire in a community sample
Authors: Striegel‐Moore Ruth H. , Perrin Nancy , DeBar Lynn , Wilson G. Terence , Rosselli Francine , Kraemer Helena C.
Published: May 2009

Objective:

To examine the operating characteristics of the Patient Health Questionnaire eating disorder module (PHQ‐ED) for identifying bulimia nervosa/binge eating disorder (BN/BED) or recurrent binge eating (RBE) in a community sample and to compare true positive (TP) versus false positive (FP) cases on clinical validators.

Method:

Two hundred and fifty‐nine screen‐positive individuals and a random sample of 89 screen negative cases completed a diagnostic interview. Sensitivity, specificity, and positive predictive value (PPV) were calculated. TP and FP cases were compared using t‐tests and Chi‐square tests.

Results:

The PHQ‐ED had high sensitivity (100%) and specificity (92%) for detecting BN/BED or RBE, but PPV was low (10 or 19%). TP and FP cases did not differ significantly on frequency of subjective bulimic episodes, objective overeating, restraint, on BMI, and on self‐rated health.

Discussion:

The PHQ‐ED is recommended for use in large populations only in conjunction with follow‐up questions to rule out cases without objective bulimic episodes. © 2009 by Wiley Periodicals, Inc. Int J Eat Disord 2010
Eating disorders in patients with obsessive–compulsive disorder: Prevalence and clinical correlates
Authors: Sallet Paulo C. , de Alvarenga Pedro Gomes , Ferrão Ygor , de Mathis Maria Alice , Torres Albina R. , Marques Andrea , Hounie Ana G. , Fossaluza Victor , do Rosario Maria Conceição , Fontenelle Leonardo F. , Petribu Katia , Fleitlich‐Bilyk Bacy
Published: May 2009

Objective:

The objective is to evaluate the prevalence and associated clinical characteristics of eating disorders (ED) in patients with obsessive–compulsive disorder (OCD).

Method:

This is a cross‐sectional study comparing 815 patients with OCD. Participants were assessed with structured interviews and scales: SCID‐I, Y‐BOCS, Dimensional Y‐BOCS, BABS, Beck Depression and Anxiety Inventories.

Results:

Ninety‐two patients (11.3%) presented the following EDs: binge‐eating disorders [= 59 (7.2%)], bulimia nervosa [= 16 (2.0%)], or anorexia nervosa [= 17 (2.1%)]. Compared to OCD patients without ED (OCD‐Non‐ED), OCD‐ED patients were more likely to be women with previous psychiatric treatment. Mean total scores in Y‐BOCS, Dimensional Y‐BOCS, and BABS were similar within groups. However, OCD‐ED patients showed higher lifetime prevalence of comorbid conditions, higher anxiety and depression scores, and higher frequency of suicide attempts than did the OCD‐Non‐ED group. Primarily diagnosed OCD patients with comorbid ED may be associated with higher clinical severity.

Discussion:

Future longitudinal studies should investigate dimensional correlations between OCD and ED. © 2009 by Wiley Periodicals, Inc. Int J Eat Disord 2010
Typical and atypical restrictive anorexia nervosa: Weight history, body image, psychiatric symptoms, and response to outpatient treatment
Authors: Santonastaso Paolo , Bosello Romina , Schiavone Paolo , Tenconi Elena , Degortes Daniela , Favaro Angela
Published: May 2009

Objective:

Few studies have examined the characteristics of atypical restrictive anorexia nervosa (AN) with a well‐powered design. The study aims to explore this issue, with particular attention paid to psychopathology and response to outpatient treatment.

Method:

The sample consists of 365 participants with restrictive AN and 204 with atypical AN. Three types of atypical AN were included: subthreshold (all the criteria except weight); partial (AN without amenorrhea); and participants with AN without fear of gaining weight.

Results:

Participants with AN without fear of weight gain reported the lowest lifetime BMI and subthreshold AN the highest. Participant with partial AN reported the highest levels of psychiatric symptoms and novelty seeking. All types of atypical AN showed high rates of dropout, whereas participants with subthreshold AN showed the highest level of full remission after treatment.

Discussion:

Before considering a revision of the diagnostic criteria of AN, further studies on adequately large samples are needed. © 2009 by Wiley Periodicals, Inc. Int J Eat Disord 2009
Radioresistant cells expressing TLR5 control the respiratory epithelium's innate immune responses to flagellin
Authors: Janot Laure , Sirard Jean‐Claude , Secher Thomas , Noulin Nicolas , Fick Lizette , Akira Shizuo , Uematsu Satoshi , Didierlaurent Arnaud , Hussell Tracy , Ryffel Bernhard , Erard Francois
Published: May 2009

Bacterial products (such as endotoxins and flagellin) trigger innate immune responses through TLRs. Flagellin‐induced signalling involves TLR5 and MyD88 and, according to some reports, TLR4. Whereas epithelial and dendritic cells are stimulated by flagellin in vitro, the cell contribution to the in vivo response is still unclear. Here, we studied the respective roles of radioresistant and radiosensitive cells in flagellin‐induced airway inflammation in mice. We found that i.n. delivery of flagellin elicits a transient change in respiratory function and an acute, pro‐inflammatory response in the lungs, characterized by TLR5‐ and MyD88‐dependent chemokine secretion and neutrophil recruitment. In contrast, TLR4, CD14 and TRIF were not essential for flagellin‐mediated responses, indicating that TLR4 does not cooperate with TLR5 in the lungs. Respiratory function, chemokine secretion and airway infiltration by neutrophils were dependent on radioresistant, TLR5‐expressing cells. Furthermore, lung haematopoietic cells also responded to flagellin by activating TNF‐α production. We suggest that the radioresistant lung epithelial cells are essential for initiating early, TLR5‐dependent signalling in response to flagellin and thus triggering the lung's innate immune responses.
Differential NKG2D binding to highly related human NKG2D ligands ULBP2 and RAET1G is determined by a single amino acid in the α2 domain
Authors: Wittenbrink Mareike , Spreu Jessica , Steinle Alexander
Published: May 2009

The activating NK cell receptor NKG2D binds to numerous stress‐induced cell surface glycoproteins with MHC class I‐related ectodomains. In humans, NKG2D ligands (NKG2DL) are members of the MHC‐encoded MIC and non‐MHC‐encoded ULBP families of proteins. The redundancy of NKG2DL raises questions about unique features associated with individual NKG2DL. The ULBP family member RAET1G contains an ectodomain highly related to ULBP2, but is unique by virtue of an extended cytoplasmic domain. Since RAET1G is poorly characterized, we studied expression and functional interactions of RAET1G in comparison to ULBP2. RAET1G transcripts were detected in most human tissues with an overall expression pattern similar to ULBP2. However, although ULBP2 strongly binds both NKG2D and the immunoevasive human cytomegalovirus glycoprotein UL16, RAET1G only weakly interacts with NKG2D and does not bind UL16. Differential binding capacities of the two highly related ectodomains are mainly due to a substitution of a conserved amino acid in the α2 domain of RAET1G. In functional terms, the reduced apparent avidity of RAET1G for NKG2D results in a less‐efficient NKG2D down‐regulation and NK degranulation. Altogether, RAET1G, like ULBP2, appears broadly expressed, but exhibits a lower apparent avidity for NKG2D due to a mutation in the center of the MHC‐like fold.
The level of B7 homologue 1 expression on brain DC is decisive for CD8 Treg cell recruitment into the CNS during EAE
Authors: Zozulya Alla L. , Ortler Sonja , Fabry Zsuzsanna , Sandor Matyas , Wiendl Heinz
Published: May 2009

DC in the CNS have emerged as the major rate‐limiting factor for immune invasion and subsequent neuroinflammation during EAE. The mechanism of how this is regulated by brain‐localized DC remains unknown. Here, we describe the ability of brain‐localized DC expressing B7‐H1 molecules to recruit CD8+ T cells to the site of inflammation. Using intracerebral microinjections of B7‐homologue 1‐deficient DC, we demonstrate a substantial brain infiltration of CD8+ T cells displaying a regulatory phenotype (CD122+) and function, resulting in a decrease of EAE peak clinical values. The recruitment of regulatory‐type CD8+ T cells into the CNS and the role of brain DC expressing B7‐homologue 1 molecules in this process open up the possibility of DC‐targeted therapeutic manipulation of neuroinflammatory diseases.
Modulation of Photochemical Properties in Ion‐Controlled Multicomponent Dynamic Devices
Authors: Barboiu Mihail , Legrand Yves‐Marie , Prodi Luca , Montalti Marco , Zaccheroni Nelsi , Vaughan Gavin , van der Lee Arie , Petit Eddy , Lehn Jean‐Marie
Published: May 2009

A bis‐pyrenyl‐terpyridine ligand 1 has been synthesised and used to prepare zinc homo‐ and heterocomplexes and their photophysical properties have been studied. Fluorescence titrations displayed modulation of absorption and emission, depending on the molarities of the ionic species (Zn2+, H+). Two single‐crystal structures give insights into the formation of multicomponent supramolecular networks, also present in solution as shown by NMR and ESI‐MS spectroscopy. NMR spectroscopy revealed fast exchanges of the ligands complexed around the metal ion, which could be reduced at lower temperature. Conformational (from W to U shape) and photophysical changes of the flexible ligand were demonstrated in the solid and liquid phases. Addition of zinc ions to the solution of ligands changes the absorption and fluorescence spectra noticeably. The zinc complexes do not form exciplexes; the fluorescence is mainly due to charge‐transfer transitions. The present work illustrates the potential use of ion‐triggered switches to generate mechanical motions that can be followed photophysically.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
A New 5,5′‐Bitetrazole Thorium(IV) Compound: Synthesis, Crystal Structure and Quantum Chemical Investigation
Authors: Pohl Roland W. H. , Wiebke Jonas , Klein Axel , Dolg Michael , Maggiarosa Nicola
Published: May 2009

Thorium(IV) 5,5′‐bitetrazolate hydrate C4H26N16O13Th has been prepared and structurally analysed by single crystal XRD. The compound crystallises in the triclinic space group P$\bar {1}$ with the cell constants a = 1058.2(2), b = 1081.6(2), c = 1136.7(2) pm, α = 73.46(2), β = 83.98(2), γ = 66.01(2)°. The observed structure is similar to the salt‐like structures of the corresponding TbIII and ErIII systems with respect to the non‐coordinating behaviour of the 5,5′‐bitetrazolate dianions. The ThIV cations form discrete hydroxo‐bridged binuclear thorium‐aqua complexes with Th–Th distances of 399(7) pm. Comparison with structural data of known hydrolysis products of the hydrated ThIV cation, and density functional calculations on gas phase molecular clusters, employing relativistic large‐core pseudopotentials and large valence‐only (7s7p5d2f1g)/[6s5p4d2f1g] basis sets for ThIV, confirm the identification of the cation in C4H26N16O13Th as [(μ‐OH)2Th2(H2O)14]6+.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
New Efficient Route to Fused Aryltetrahydroindolizinones via N‐Acyliminium Intermediates
Authors: Chiurato Matteo , Routier Sylvain , Troin Yves , Guillaumet Gérald
Published: May 2009

Straightforward routes to fused tetrahydroindolizinones by two routes A and B, starting either from 2‐formylbenzoic acid and esters or from β‐hydroxy lactones via acyl iminium ions, are described. A plausible mechanism and limitations are given. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Capillary gel electrophoresis of therapeutic oligonucleotides – Analysis of single‐ and double‐stranded forms
Authors: Székely László , Kiessig Steffen , Schwarz Maria A. , Kálmán Franka
Published: May 2009

Recently, several therapeutic double‐stranded (ds) oligonucleotides (ODNs) are in pharmaceutical development. During quality control, these therapeutic molecules have to be characterized with respect to their identity, their content and their impurity profile. It follows that the ds molecule as well as its process‐ and product‐related impurities have to be quantified. The single strands are considered as process as well as product‐related impurities in the ds drug substance. Applying well known, conventional, single‐base resolution CE‐CGE systems developed for the quality control of single‐stranded antisense ODNs in the early 1990s, it turned out that the ds ODNs under investigation are migrating in broad, splitted peaks between the peaks reaction zones are observed. It follows that the quantification of the single strands in the drug substance as well as quantification of other product‐related impurities, e.g. n‐1; n‐2 (loss of one and two bases (n), respectively) etc., are not possible without adaptation of the test system. The paper shows how the test system was adjusted in order to determine single‐stranded strands as well as ds strands next to each other quantitatively in the ds drug substance under investigation.
Analysis of nerve agent degradation products in high‐conductivity matrices by transient ITP preconcentration and CZE separation coupled to ESI‐MS
Authors: Lagarrigue Mélanie , Bossée Anne , Bégos Arlette , Delaunay Nathalie , Varenne Anne , Gareil Pierre , Bellier Bruno
Published: May 2009

Preconcentration of nerve agent degradation products (alkyl methylphosphonic acids) contained in high‐conductivity matrices was performed using transient ITP to enhance sensitivity of CE‐ESI‐MS. The separation conditions of the five studied alkyl methylphosphonic acids in CE‐MS were first optimized. The presence of methanol in the separation medium was required to obtain a good separation of the analytes under counter‐EOF conditions. Preconcentration by ITP was induced by the BGE acting as leading electrolyte (LE) while the terminating electrolyte (TE) was loaded before the sample because of the counter‐EOF conditions. Different leading ions (formate or acetate) and LE concentrations were tested. The best results for the analysis of soil extracts fortified with the analytes were obtained with an LE composed of 30 mM CH3COONH4 adjusted to pH 8.8 with ammonium hydroxide in (35:65 v/v) MeOH/H2O mixture. The TE consisted of 200 mM glycine adjusted to pH 10.0 with ammonium hydroxide in the same solvent mixture. The loading length of the TE zone was optimized. The initial pH of the TE, which determined the initial mobility of the terminating ion, appeared to markedly influence the resolution and the sensitivity. This transient ITP‐CZE‐MS method was then adapted for the analysis of rat urine samples fortified with the analytes, which required the use of a more concentrated LE (50 mM). LODs between 4 and 70 ng/mL in soil extract, and between 5 and 75 ng/mL in rat urine were reached from extracted ion electropherograms.
Proteomics in globe artichoke: Protein extraction and sample complexity reduction by PEG fractionation
Authors: Acquadro Alberto , Falvo Sara , Mila Silvia , Giuliano Albo Alessandra , Comino Cinzia , Moglia Andrea , Lanteri Sergio
Published: May 2009

Here, we report the first leaf proteome analysis for globe artichoke. Three protein extraction protocols were tested and a reproducible Mg/NP‐40‐based method was established. Ribulose‐1,5‐biphosphate carboxylase‐oxygenase (RuBisCO) is a highly abundant leaf protein, and its presence masks co‐localizing, less abundant proteins. To remove RuBisCO from the sample, and thereby improve spot resolution, a PEG fractionation approach was elaborated. 2‐DE profiles of various PEG fractions showed that the fractionation procedure was successful in excluding most of the RuBisCO, allowing for the detection of many low‐abundance proteins. Western blot analysis was able to confirm the reduction in RuBisCO content achieved by PEG fractionation. In all, 841 distinct protein spots were detected, and 40 of these, selected from the RuBisCO region of the 2‐DE profile, were successfully identified by MS. A number of homologues of these proteins also co‐localize with RuBisCO in Arabidopsis thaliana.
Highly resolved separation and sensitive amperometric detection of amino acids with an assembled microfluidic device
Authors: Zhai Chun , Qiang Wei , Lei Jianping , Ju Huangxian
Published: May 2009

An assembled microfluidic device (AMD) was constructed for highly resolved separation and sensitive amperometric detection of amino acids. In the AMD three polymer retainers were integrated with a quartz capillary and a copper microdisk electrode. A facile ultrasonic method was suggested for the preparation of sampling fracture on the capillary. The fracture led to separation efficiency up to 340 000 plates/m and improved greatly the sensitivity for amino acid detection in an 8 cm long quartz capillary. At a sampling voltage of 100 V for 2 s and a separation voltage of 1800 V (225 V/cm) within 300 s, the linear ranges of 12 amino acids determination at +0.8 V (versus Ag/AgCl) were from 12, 20, 17, 27, 31, 44, 25 and 45 to 750 μM for tryptophan, phenylalanine, methionine, valine, threonine, alanine, serine and glycin, and 4.6, 17, 16 and 49 μM to 1.0 mM for lysine, proline, leucine and tyrosine with the detection limit (S/N=3) down to 1.4 μM for lysine. The designed AMD could be successfully applied to analyze amino acids in beverage samples with recovery from 97.8 to 105.2%, indicating its advantages and potential analytical application in different fields.
An accessible micro‐capillary electrophoresis device using surface‐tension‐driven flow
Authors: Mohanty Swomitra K. , Warrick Jay , Gorski Jack , Beebe David J.
Published: May 2009

We present a rapidly fabricated micro‐capillary electrophoresis chip that utilizes surface‐tension‐driven flow for sample injection and extraction of DNA. Surface‐tension‐driven flow (i.e. passive pumping) [G. M. Walker et al., Lab. Chip. 2002, 2, 131–134] injects a fixed volume of sample that can be predicted mathematically. Passive pumping eliminates the need for tubing, valves, syringe pumps, and other equipment typically needed for interfacing with microelectrophoresis chips. This method requires a standard micropipette to load samples before separation, and remove the resulting bands after analysis. The device was made using liquid phase photopolymerization to rapidly fabricate the chip without the need of special equipment typically associated with the construction of microelectrophoresis chips (e.g. cleanroom) [A. K. Agarwal et al., J. Micromech. Microeng. 2006, 16, 332–340; S. K. Mohanty et al., Electrophoresis 2006, 27, 3772–3778]. Batch fabrication time for the device presented here was 1.5 h including channel coating time to suppress electroosmotic flow. Devices were constructed out of poly‐isobornyl acrylate and glass. A standard microscope with a UV source was used for sample detection. Separations were demonstrated using Promega BenchTop 100 bp ladder in hydroxyl ethyl cellulose (HEC) and oligonucleotides of 91 and 118 bp were used to characterize sample injection and extraction of DNA bands. The end result was an inexpensive micro‐capillary electrophoresis device that uses tools (e.g. micropipette, electrophoretic power supplies, and microscopes) already present in most labs for sample manipulation and detection, making it more accessible for potential end users.
Investigation of C‐reactive protein binding to phosphatidyl choline by CZE and ESI‐Mass analysis
Authors: Peng Yu‐Non , Ho Yu‐Ling , Wu Chung‐Yu , Liu Mine‐Yine
Published: May 2009

A simple CZE has been developed to investigate the binding reactions between C‐reactive protein (CRP) and native as well as Cu2+ oxidized phosphatidyl choline (PC) in this study. An aqueous‐organic solvent system containing 20% sodium phosphate, 70% methanol and 10% acetonitrile was selected as the optimal CZE separation buffer. Native PC showed a broad, higher mobility major peak and a sharp, lower mobility minor peak. Oxidized PC (ox‐PC) appeared as two adjacent peaks. PC bound to CRP in the presence of metal ions Ca2+ and Mg2+. The absorbance at 214 nm for PC+CRP was about five times of that for PC. Surprisingly, ox‐PC interacted much more weakly with CRP. The absorbance at 214 nm for ox‐PC+CRP was close to that of ox‐PC. Meanwhile, ESI‐Mass analysis also suggested that four PC molecular species (C16:0/C18:1, C16:0/C18:2, C18:0/C18:2, C18:0/C18:1) bound with CRP since the ion intensities of PC+CRP were lower than that of PC alone. This study uses both CZE and ESI‐Mass analysis to characterize the interaction between CRP and native as well as Cu2+ oxidized PC, and provides new analytical methods for determining the binding reactions. In addition, it also gives new insight into the molecular interactions between CRP and native as well as oxidized PC.
Rapid microfluidic separation of magnetic beads through dielectrophoresis and magnetophoresis
Authors: Krishnan Jegatha Nambi , Kim Choong , Park Hyun Jik , Kang Ji Yoon , Kim Tae Song , Kim Sang Kyung
Published: May 2009

We present the design and fabrication of a new microfluidic device in which the dielectrophoresis and magnetophoresis phenomena were used for the separation of the superparamagnetic microbeads of different sizes. By exploiting the fact that two different particles can exhibit different dielectrophoretic force–frequency spectra, we utilize this device to perform multiplex detection from a single sample solution. We found the transition frequency range for 1, 2.8, and 4.5 μm magnetic beads using our device. Bead‐based analysis revealed that a high separation efficiency (∼90%) could be obtained from a single sample solution containing both 4.5 and 2.8 μm beads. The average flow velocity of the beads was maintained at 9.8 mm/s, enabling fast analysis with a smaller amount of reagents. The magnetic field distribution on the beads and the bead flow at the channel cross section for different dielectrophoretic conditions was obtained using CFD‐ACE+ simulation. Issues relating to the fabrication and operation of the device are discussed in detail. Finally, we demonstrated the feasibility of parallel detection/trapping of different beads on the same chip. This separation approach offers the performance of multiplex analysis in lab‐on‐a‐chip devices.
Design and integration of eco‐industrial parks for managing water resources
Authors: Lovelady Eva M. , El‐Halwagi Mahmoud M.
Published: May 2009

This work is aimed at developing an optimization‐based approach to the design and integration of eco‐industrial parks (EIPs). Focus is given to the management of water among multiple processes in a common EIP facility. Recycle, reuse, and separation using interception devices are considered as possible strategies for managing wastewater. A source‐interception‐sink structural representation is used to embed potential configurations of interest. The representation accounts for the possibilities of direct recycle, material (waste) exchange, mixing and segregation of different streams, separation and treatment in interception units, and allocation to process users (sinks). Then, the EIP design problem is formulated as an optimization program whose objective is to minimize cost of the EIP while determining optimal recycle and separation strategies. A case study is solved to illustrate the applicability of the devised approach. © 2009 American Institute of Chemical Engineers Environ Prog, 2009
Immunohistochemical expression of interleukin‐4, ‐6, ‐8, and ‐12 in inflammatory cells in surrounding invasive front of oral squamous cell carcinoma
Authors: de Oliveira Marcos Vinícius Macedo , de Carvalho Fraga Carlos Alberto , Gomez Ricardo Santiago , Paula Alfredo Maurício Batista D.
Published: May 2009

Background

Cytokines play important roles in the diverse interactions between tumor microenvironment and malignant cells. This study evaluated the association of interleukin (IL)‐4, ‐6, ‐8, and ‐12 expressions and clinicopathologic parameters of 35 primary oral squamous cell carcinomas (OSCCs).

Methods

Patients were staged according to the TNM clinical staging. Malignancy grading of invasive front was evaluated in hematoxylin‐eosin (H&E)‐stained slides. Immunohistochemical technique was performed on frozen tissue sections. Association between clinicopathologic parameters and IL expression were analyzed using nonparametric Kruskal‐Wallis (α = 0,05) and Mann‐Whitney U tests, with Bonferroni correction. Correlations between interleukins were analyzed by the Spearman coefficient.

Results

Expression of ILs was verified in all samples; however, this finding was not related to clinicopathologic parameters. It was not the observed correlation between ILs.

Conclusions

Expression of IL‐4, ‐6, ‐8, and ‐12 in the invasive front of OSCC is not involved with the clinicopathologic parameters of the disease. © 2009 Wiley Periodicals, Inc. Head Neck, 2009
Prognostic significance of molecular markers in oral squamous cell carcinoma: A multivariate analysis
Authors: Shah Neelam G. , Trivedi Trupti I. , Tankshali Rajen A. , Goswami Jignesh V. , Jetly Dhaval H. , Shukla Shilin N. , Shah Pankaj M. , Verma Ramtej J.
Published: May 2009

Background

Multiple marker accumulation impacts tumor progression and biologic phenotypes affect clinical outcome of patients with head and neck cancer. Hence, this study investigated a battery of molecular markers that may help to reflect biologic aggressiveness and predict prognosis.

Methods

Epidermal growth factor receptor (EGFR), Stat3, H‐ras, c‐myc, p53, cyclin D1, p16, Rb, Ki‐67, and Bcl‐2 were localized immunohistochemically in 135 oral squamous cell carcinoma patients to assess prognostic value.

Results

In univariate analysis of total patients, p53, Stat3, and p16 predicted both relapse‐free survival (RFS) and overall survival (OS). In Cox multivariate analysis, after adjusting for tumor size, nodal status, and lymphatic permeation, p53 was independently associated with RFS and OS, and p16 with RFS only. In only early‐stage patients, in univariate analysis, nuclear Stat3 was significant for RFS and OS.

Conclusion

Immunostaining of p53, p16, and Stat3 might serve as potential adjuncts in pathologic evaluation of oral tumors to predict risk of relapse. © 2009 Wiley Periodicals, Inc. Head Neck, 2009
Concentration–discharge relationships reflect chemostatic characteristics of US catchments
Authors: Godsey Sarah E. , Kirchner James W. , Clow David W.
Published: May 2009

Concentration–discharge relationships have been widely used as clues to the hydrochemical processes that control runoff chemistry. Here we examine concentration–discharge relationships for solutes produced primarily by mineral weathering in 59 geochemically diverse US catchments. We show that these catchments exhibit nearly chemostatic behaviour; their stream concentrations of weathering products such as Ca, Mg, Na, and Si typically vary by factors of only 3 to 20 while discharge varies by several orders of magnitude. Similar patterns are observed at the inter‐annual time scale. This behaviour implies that solute concentrations in stream water are not determined by simple dilution of a fixed solute flux by a variable flux of water, and that rates of solute production and/or mobilization must be nearly proportional to water fluxes, both on storm and inter‐annual timescales. We compared these catchments' concentration–discharge relationships to the predictions of several simple hydrological and geochemical models. Most of these models can be forced to approximately fit the observed concentration–discharge relationships, but often only by assuming unrealistic or internally inconsistent parameter values. We propose a new model that also fits the data and may be more robust. We suggest possible tests of the new model for future studies. The relative stability of concentration under widely varying discharge may help make aquatic environments habitable. It also implies that fluxes of weathering solutes in streams, and thus fluxes of alkalinity to the oceans, are determined primarily by water fluxes. Thus, hydrology may be a major driver of the ocean‐alkalinity feedback regulating climate change. Copyright © 2009 John Wiley & Sons, Ltd.
Comparison and modification of equations for calculating evapotranspiration (ET) with data from Gansu Province, Northwest China
Authors: Zhai Luxin , Feng Qi , Li Qisen , Xu Cundong
Published: May 2009

A total of 11 empirical evapotranspiration equations were developed by Hargreaves (1975), Hargreaves (1985), Makkink, Turc, Priestley–Taylor, Jensen–Haise, Doorenbos and Pruitt, Abtew, McGuinness and Bordne, Rohwer and Blaney–Criddle. These were compared with pan evaporation data measured at 10 stations in Gansu Province, northwest China. The comparison was first made using the default values in each of the 11 equations, and then redone using calibrated coefficient values. The calibration was made for all 11 equations using the climatic index Pa/Pg. The results show that using default coefficient values resulted in large errors for all equations. The largest error was found in the comparison results of the Turc, and McGuinness and Bordne equations. The Turc and Jensen–Haise equations should be used to estimate the daily evapotranspiration (ET) under the conditions of Tmean > 0 and Tmean > −3°C, respectively, when applied to northwest China. Based on the comparison results of before and after recalibration, the Doorenbos and Pruitt method is more suitable to the arid, semiarid and wet regions in northwest China. The accuracy of the results for determining monthly ET greatly improved when calibrated coefficient values were introduced to the 11 equations, except for McGuinness and Bordne, Abtew, and Blaney–Criddle, which need to be recalibrated using two parameters. Thus, it can be concluded that calibration can be used to modify evapotranspiration equations with multi‐station data to improve the accuracy of evapotranspiration estimates in northwest China. Copyright © 2009 John Wiley & Sons, Ltd.